Research Article Characterization of Complexes Synthesized ...downloads.hindawi.com/archive/2014/736538.pdf · Research Article Characterization of Complexes Synthesized Using Schiff

Research ArticleCharacterization of Complexes Synthesized Using SchiffBase Ligands and Their Screening for Toxicity Two Fungal andOne Bacterial Species on Rice Pathogens

T Mangamamba1 M C Ganorkar1 and G Swarnabala23

1 Agarwal Siksha Samiti Charminar Hyderabad 500 002 India2 Shadan PG Institute Khairatabad Hyderabad 500 001 India3 Centre for Materials for Electronics Technology (C-MET) IDA Phase III Cherlapally (HCL PO) Hyderabad 500 051 India

Correspondence should be addressed to G Swarnabala swarnabalagantigmailcom

Received 22 February 2014 Revised 8 May 2014 Accepted 9 May 2014 Published 18 September 2014

Academic Editor Alfonso Castineiras

Copyright copy 2014 T Mangamamba et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Coordination complexes with metal ions Cu(II) Ni(II) Co(II) Fe(III) Mn(II) Cr(III) and VO(II) with six ligands formed bycondensation products using azides and aldehydes or ketones are characterized Both the ligands and the complexes synthesizedare characterized by C H N Cl and metal analyses IR UV-Vis TGA and magnetic susceptibility for tentative structureproposal Several of them are screened for their toxicity (ie physiological activity) against fungal species Rhizoctonia solani andAcrocylindrium oryzae and a bacterium Xanthomonas oryzae on rice pathogens The study shows that the observed physiologicalactivity is enhanced for the metal complexes as compared to the simple metal salts or ligands except in the case of L3 or HAEPligand where the free ndashOH and ndashNH

2groups on the ligand seemed to have inhibited the activity It is also observed that the order

of activity has a dependence on the increased atomic weight of the metal ion in use In some cases especially the VO(II) complexesthey are found to be better than the standards in use both for the fungicides and for the bactericide

1 Introduction

Ever since the Italian chemist Hugo Schiff used imines tomake several ldquometallo-iminesrdquo numbers of variants of thecondensation products of imines and aldehydes or ketonessuch as RCH=NR1015840mdashwhere R amp R1015840 are alkyl andor aryl sub-stituentrsquos are popularizedThey are also known as Schiff bases(SBs) anils imines or azomethines They are also known asanils imines or azomethinesThese have several applicationsin organic studies such as for building new heterocyclicsystems for identification detection and determination ofaldehydes and ketones for purification of carbonyl or aminocompounds or for the protection of these groups during thecomplex formation or such sensitive reactions [1] They haveother side applications in various other fields coordinationchemistry [2ndash9] analytical chemistry [10ndash16] pigments anddyes [17] and polymer industries [18] in vitamins andenzymes [4] for model biomolecules There is a special

mention of these complexes in agriculture [4] as fungicidespesticides and bacteriocides

Survey of the literature for SB metal complexes andtheir applications showed excellent review articles [19 20]for the detailed understanding of this class of compoundsin all respects and one more especially dedicated tocopper complexes [21] They provide several details onnumber of metal complexes derived from SBs used widelyfor applications in food and dye industry analyticalchemistry catalysis polymers antifertility agrochemicalanti-inflammatory activity antiradical activities andbiological systems as enzymatic agents Several havereviewed them in light of their antimicrobial antibacterialantifungal antitumor and cytotoxic activities [19 20] Thereare some individual articles too not mentioned in themwith studies on the above mentioned types of activities withsome metals ions such as Cu(II) Ni(II) and Co(II) with SBderived from salicylaldehyde and 2-substituted aniline [22]

Hindawi Publishing CorporationInternational Journal of Inorganic ChemistryVolume 2014 Article ID 736538 22 pageshttpdxdoiorg1011552014736538

2 International Journal of Inorganic Chemistry

Cu(II) Ni(II) and Zn(II) complexes with SB from p-chloro-benzaldehyde with p-chloroaniline [23] Mn(II) Fe(II)Ni(II) and Cu(II) complexes with SB from 5-acetamido-134-thiodiazole-2-sulphonamide and their biologicalactivity [24] Zn(II) Ni(II) and Cu(II) complexes withSB from dicinnamoylmethane and aromatic amines [25]Zn(II) Mn(II) Ni(II) and Cu(II) complexes with SB from2-hydroxy-1-naphthaldehyde and 5-amino-1-naphthol andtheir antibacterial activities [26] Co(II) Ni(II) and Cu(II)complexes with SB from 14-dicarbonylphenyldihydrazidewith 26-diformyl-4-methylphenol [27] Co(II) Ni(II)and Cu(II) complexes with SB from 2-HClBr-6-(4-fluorophenyliminomethyl)phenol [28] Co(II) Ni(II)and Cu(II) complexes with SB from pyrazolealdehydewith 2-aminophenol [29] Co(II) Ni(II) Zn(II) Cd(II)Hg(II) and Cu(II) complexes with SB from benzofuran-2-carbohydrazide and 4-methyl-thio-benzaldehyde andtheir antifungal antibacterial activities being screened[30] Ni(II) and Cu(II) complexes of SB derived from 1-naphthylamine and 2-hydroxy-naphthalene-1-carbaldehyde[31] Fe(III) Ni(II) Cu(II) Co(II) Zn(II) and UO

2(II)

complexes of SB derived from 2-furancarboxaldehyde and o-phenylenediamine [32] VO(II) Co(II) Rh(III) Pd(II) andAu(III) complexes of SB derived from 4-nitrobenzoicacid and thiosemicarbazide and their antibacterialactivity [33] VO(IV) Cu(II) and Ru(II) complexes ofSB derived from 3-hydroxyquinoxaline-2-carboxaldehydeand several amines 18-diaminonaphthalene 23-diaminemaleonitrile 12-diaminocyclohexane 2-iminophenol and4-aminoantipyrine [34] Mn(II) Co(II) Ni(II) Cu(II) andZn(II) complexes of SB derived from 1 10-phenanthrolineand o-vanillidene-2-aminobenzothiazole and o-vanillidene-2-quino-N-(2-pyridyl)-benzenesulfonamide [35] Hg(II)Zn(II) and VO(IV) complexes of SB from S-aminosulfonyl-4-chloro-N-26-dimethylphenyl-2-hydroxybenzamide withsalicylamide [36] Co(II) Cu(II) Ni(II) and Zn(II)complexes of SB derived from several substitutedpyridines with salicylaldehyde [37] Recently new seriesof Co(II) Ni(II) Cu(II) Cd(II) and Hg(II) complexeswere synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime The ligand alongwith its metal complexes has been characterized on thebasis of analytical data IR electronic mass 1HNMR ESRspectral data thermal studies magnetic susceptibility andmolar conductance measurements In order to evaluate theeffect of metal ions upon chelation both the ligand and itsmetal complexes were screened for their antibacterial andantifungal activities by minimum inhibitory concentration(MIC) method [38] Metal chelates [M(HL)

2(H2O)2]X2

(where M = Mn(II) Co(II) Cu(II) Ni(II) or Zn(II) X =NO3

minus or Clndash and HL = SB moiety) have been preparedand characterized by elemental analysis magnetic andspectroscopic measurements (infrared X-ray powderdiffraction and scanning electron microscopy) The SBand its metal chelates have been screened for their in vitroantibacterial activity against four bacteria gram-positive(Staphylococcus aureus) and gram-negative (Escherichiacoli) and two strains of fungus (Aspergillus flavus andCandida albicans) The metal chelates were shown to

possess more antibacterial activity than the free SB chelate[39]

Metal complexes of SBs derived from 2-furancarboxal-dehyde and o-phenylenediamine (L1) and 2-thiophenecar-boxaldehyde and 2-aminothiophenol (HL2) are reported andcharacterized based on elemental analyses IR 1H NMRsolid reflectance magnetic moment molar conductance andthermal analysis (TGA) ConsiderM = Fe(III) Ni(II) Cu(II)Co(II) Zn(II) andUO2(II)The synthesized ligands in com-parison to their metal complexes were also screened for theirantibacterial activity against bacterial species Escherichiacoli Pseudomonas aeruginosa and Staphylococcus Pyogenesas well as fungi (Candida) The activity data show the metalcomplexes to be more potent antibacterials than the parentSB ligand against one or more bacterial species [32]

Synthesis and characterisation of new transition metalcomplexes of SBs derived from 3-hydroxyquinoxaline-2-carboxaldehyde and application of some of these complexesas hydrogenation and oxidation catalysts The subnormalmagnetic moment values substantiate a binuclear structurefor all the Cu(II) complexes favouring square-planar geom-etry and those with magnetic moment of 176 BM favouredoctahedral geometry with mononuclear complex formationwith this SB ligand [34]

It is found that the SBs selected for synthesis for this studyhave not been found in the literature It is also noticed thatmany of the tridentate ligands are found to show strikingbiochemical characters where the azomethine linkage areblended into stable structured inorganic metal chelates In adelicately balanced living system physiological activity is aresult of several chemical and physical processes In such pro-cesses the metal complexes furnished useful drugs and othersubstances as described by selective toxicity in pharmacology[40ndash42] They function by upsetting this delicate balance intwo ways (a) by reinforcing the toxicity of a heavy metalandor (b) by withdrawing the essential metal content fromthe system For example in highly basic iron rich soils themetal ion not available to the rootlets of plants is extractedby spraying Ethylenediaminetetraacetic acidmdash(edta) in theform of a soluble complex Such a mechanism for manyfungicides and bactericides is described as a partition effector cooperative effect [43] Thus to evaluate the chemicalsubstances as fungicides and bactericides the followingmethods are used commonly (1) slide germination method[44ndash46] (2) test-tube dilution method [47] (3) cell-volumeassaymethod [48] (4) inhibition-zone ormodified paper discmethod [49ndash51] and (5) poisoned food technique [50]

Three important rice pathogens were selected for thepresent study two fungal species and a bacterium Thereasons for selecting these species are given in brief (1)Rhizoctonia solani causes sheath blight [52 53] which is aserious disease of the rice-cropThe symptoms are (a) grayishwhite patches and (b) yellowing of leaves This spreads veryquickly and causes enormous loss It also causes severalother diseases on many economically important commercialcrops (2) Acrocylindrium oryzae causes sheath rot of paddydecaying the sheath and was first reported [54ndash56] in IndiaA large number of fungicides are evaluated against thisorganism in vitro and in vivo A few of them are in use to

International Journal of Inorganic Chemistry 3

arrest the disease yet it is quite uncontrolled (3)Xanthomonasoryzae causes bacterial-leaf-blight and is usually noticed [54ndash56] in the field at the heading stage The young seedlingsafter transplanting are affected when the upper leaves arerolled along the mid-rib to wither away Subsequently thedisease extends to the whole field giving a burnt appearanceApplications of heavy doses of nitrogenous fertilizers are saidto be the cause of this disease

In this paper we report the synthesis of new SBs andtheir metal complexes They were characterized by C HN Cl and metal analyses Infra-red (IR) UV-Visible (UV-Vis) thermogravimetric analysis (TGA) for estimating coor-dinated water and magnetic susceptibility measurementsBy using the appropriate techniques or methods these werescreened for their toxicity against the chosen fungal andbacterial organisms The results are summarized in the lightof their observed physiological activity and a scope for futuredevelopment

2 Materials and Methods

21 Solvents and Reagents Solvents were purified and dis-tilled as per standard procedures [57] Benzoic acid hydrazideor benzohydrazide [58 59] 2-hydroxybenzohydrazide or sal-icylhydrazide [60 61] and 1-(24-dihydroxyphenyl)ethanoneor resacetophenone [62]were prepared as per reported proce-dures Hydrazine carbothioamide or thiosemicarbazide wasrecrystallized from water The sodium salt of dehydroaceticacid or 3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one [63]was used as a white solid after treating with dil HCl

22 SBs Ligands Synthesized Are the Following (Scheme 1)

(1) BHFH or Ligand 1 (L1) = N1015840-furan-2-yl) methy-lene)-2-hydroxybenzohydrazide was obtained bycondensing salicylhydrazide or 2-hydroxybenzohy-drazide and furfuraldehyde or furan-2-carbaldehyde

(2) BHEH or Ligand 2 (L2) = 2-hydroxy-N1015840-(1-(24-dihydroxyphenyl)ethylidene) benzohydrazide) wasobtained from salicylhydrazide or 2-hydroxybenzo-hydrazide and resacetophenone or 1-(24-dihydroxy-phenyl)ethanone

(3) HAEP or Ligand 3 (L3) = 1-(1-(2 4-dihydroxyphenyl)ethylidene thiosemicarbazidewas obtained fromhyd-razinecarbothioamide or thiosemicarbazide and resa-cetophenone or 1-(2 4-dihydroxy phenyl)ethanone

(4) BFH or Ligand 4 (L4) = N1015840-((furan-2-yl) methy-lene)benzohydrazide was obtained from benzohy-drazide and furfuraldehyde or furan-2-carbaldehyde

(5) BHDH or Ligand 5 (L5) = 2-hydroxyl-N1015840-(1-(2-hydroxy-6-methyl-4-oxo-4H-pyran-3-yl)ethylidene)benzohydrazide was obtained from salicylhydrazideor 2-hydroxybenzohydrazide and dehydroacetic acidor 3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one

(6) DHA or Ligand 6 (L6) = 3-acetyl-2-hydroxy-6-me-thyl-4H-pyran-4-one or dehydroacetic acid was usedas it is

23 Physical Measurements C H and N analyses were doneon Perkin-Elmer 240C analyzer IR spectra were recordedon Perkin-Elmer grating spectrophotometer 577 near IR-Vis-UV spectra were recorded on DMR-21 in absorbance rangeof 300ndash2000 nm Magnetic susceptibilities were determinedat RT on Faradayrsquos balance The metal and chloride wereestimated by gravimetry [64] The TGA were analyzed instatic air using limiting temperature of 500∘C and heatingrate of 10∘Cmin

24 Preparation of the Complexes All the complexes wereprepared by a very similar procedure to the metal chloride(except VO(II) being a sulfate) inmethanol respective liganddissolved in methanol is added slowly while stirring Thismixture was either refluxed for 30min to 3 hrs or digestedfor 1-2 h for different complexes [52] Some complexes wereobtained at pH 55 and some around 85 depending on thebasicity of the ligand in use Quantitative precipitates werecollected washed and dried

The relevant physical data such as C H N Cl meltingpoints or decomposition temperatures colour and metalanalyses are compiled for each ligand and its complexes inTables 1 2 3 4 5 and 6 For easy comparison and predictionof the complex formation with clarity on the denticity of theligand interpretation of the IR data of each ligand and itscomplexes are presented separately in Tables 7ndash12 with allthe relevant explanation and references The analysis of themagnetic susceptibility measurements the bands obtainedusing the UV-Vis spectra their transitions the predictedgeometries and the interpreted molecular structures arediscussed separately for convenience in Tables 13ndash19 for eachmetal ion forming complex with different ligands

25 Physiological Activity For the fungal species liquid brothmethod [52] was followed peeled and cooked potato (350 g)was collected into which dextrose (35 g) was dissolved andmade up to 1750mL by distilled water (PDA medium) pHwas adjusted to 70 by adding drops of NaOH solution Itwas distributed as 100mL each into seventeen 250mL conicalflasks containing 2 g of agar-agar and 100mg metal complexfor the organism Rhizoctonia solani For the Acrocylindriumoryzae it was distributed as 25mL each into 70 (150mL) con-ical flasks containing 25mg of themetal complex (1000 ppm)

All the flasks were tightly plugged with cotton andpaper They were all sterilized in the autoclave at 15 lbspressure and 121∘C for 20min The sterilized molten PDAmedium from each flask with the metal complex suspendeduniformly was poured into five petri dishes (90mmdiameterand 20mL each) and all the replicates were numbered andlabeled immediately All these specimenswere inoculated andincubated along with a standard fungicide Dithane M-45for comparison Control flasks without chemical were alsoinoculated and incubated simultaneously

In the case of the bacterium well-zone or inhibition-zone technique [49 51] was adopted To hot 1 L distilledwater Haywardrsquos medium [49ndash52] was added while stirringThe solution was made up to 2 L and pH adjusted to 70 byadding drops of NaOH solution It was distributed equally


C

OH

OH

HN

O

+

+

OC

H

O

C

OH

OH

OH

OHOH

OHOH

OH

OH

OH

OH

NH

O

N C

H

O

CHN

O

CO

C NH

NH

NH

O

N C

OH

CHN

O

+

OC

H

O

C

O

N C

H

O

CHN

S

+ CON CC

S

C HN

O

+

OHO

HO

O

CO

C

OH

HN N

OO

O

C

2-Hydroxybenzohydrazide Furan-2-carbaldehyde

2-Hydroxybenzohydrazide 1-(24-dihydroxyphenyl)ethanone 2-Hydroxy- -(1-(24-dihydroxyphenyl)ethylidene)benzohydrazide

Thiosemicarbazide

1-(24-dihydroxyphenyl)ethanone 1-(1-(24-dihydroxyphenyl)ethylidene)thiosemicarbazide

Benzohydrazide Furan-2-carbaldehyde -((Furan-2-yl)methylene)benzohydrazide

2-Hydroxybenzohydrazide

3-Acetyl-2-hydroxy-6-methyl-4H-pyran-4-one

2-Hydroxy- -(1-(2-hydroxy-6-methyl-4-oxo-4H-pyran-3-yl)ethylidene)benzohydrazide

L2

L1

L3

L4

L5

BHFH

BHFH

HAEP

BFH

BHDH

O

O

C ODehydroacetic acid (DHA) or3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one

L6

NH2

NH2

NH2

NH2

NH2

minusH2O

minusH2O

minusH2O

minusH2O

minusH2O

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

-((Furan-2-yl)methylene)-2-hydroxybenzohydrazide

H2N

H3C

H2N

N998400

N998400

N998400

N998400

Scheme 1


Table 1 Elemental composition and physical data of BHFH ligand and its complexes

S number Complex Mpt∘C Colour C H N M Cl Mol Wt

gm RemarksObserved (calculated)

1 BHFH-L1(C12H8N2O3)

210 White 6300(6318)

450(438)

1256(1227) mdash mdash 22813 Loss of 2H

2 [Cu(BHFH)]2-pH 55ndash70Cu2C24H16N4O6

308 Grey 5002(5010)

290(278)

1000(973)

2095(2209) mdash 57535 Loss of 8H

3 [Cu(BHFH)H2O]-pH 85CuC12H10N2O4

280 Green 4720(4744)

345(329)

950(922)

2000(2094) mdash 30355 Loss of 8H

4 [Ni(BHFH)H2O]-pH 55ndash70NiC12H10N2O4

265 Red 5000(5025)

350(349)

920(976)

2000(2047) mdash 28683 Loss of H2O

5 [Ni(BHFH)2]-pH 85NiC24H16N4O6

280 Green 5600(5617)

400(390)

1100(1092)

1150(1145) mdash 51270 Loss of 6H

6 [Co(BHFH)(H2O)Cl]2Co2C24H20N4O8Cl2

260 Pink 4255(4270)

330(326)

851(829)

1750(1746)

1050(1052) 67512 Loss of 8H

7 [Fe(BHFH)Cl2]2Fe2C24H16N4O8Cl4

320 Red 4050(4058)

280(282)

792(789)

1600(1574)

2000(2001) 70970 Loss of 4H

8 [Mn(BHFH)(H2O)Cl]2Mn2C24H20N4O8Cl2

280 Yellow 4450(4465)

298(310)

812(868)

1700(1690)

1000(1101) 64500 Loss of 15H2O

9 [VO(BHFH)Cl]2V2C24H16N4O8Cl2

285 Grey 4400(4414)

300(306)

850(857)

1500(1560)

1074(1087) 65314 Loss of 8H

Table 2 Elemental composition and physical data of BHEH ligand and its complexes



1 BHEH-L2(C15H13N2O4)

215 Yellow 6300(6318)

500(491)

989(982) mdash mdash 28516 Loss of H

2 [Cu(BHEH)Cl]CuC15H13N2O4Cl

305 Green 4705(4736)

350(342)

750(737)

1600(1672)

950(935) 38010 Loss of 4H

3 [Ni(BHEH)2]NiC30H26N4O8

270 Red 5700(5726)

420(414)

877(891)

950(934) mdash 62870 Loss of 2H

4 [Co(BHEH)2]CoC30H28N4O8

260 Brown 5750(5761)

435(448)

901(896)

1000(943) mdash 63093 mdash

5 [Fe(BHEH)(H2O)Cl]2Fe2C30H30N4O10Cl2

305 Black 4555(4564)

435(380)

723(710)

1452(1416)

950(900) 78870 Loss of 2H

6 [Mn(BHEH)2]MnC30H26N4O8

285 Brown 5800(5802)

393(387)

900(902)

1000(878) mdash 62050 Loss of 4H

7 [VO(BHEH)Cl]2V2C30H26N4O10Cl2

300 Grey 4420(4428)

329(334)

725(738)

1286(1343)

920(946) 75888 Loss of 2C and 2H

Table 3 Elemental composition and physical data of HAEP ligand and its complexes



1 HAEP-L3(C9H11N2O2S)

193 Brown 5200(5218)

540(531)

1330(1352) mdash mdash 20716 Loss of NH2 and 2H

2 [Cu(HAEP)]2Cu2C18H18N6O4S2

310 Brown 4000(4021)

350(335)

1550(1564)

2400(236) mdash 53722 Loss of 2NH2 and 2OH

3 [Ni(HAEP)2]Ni2C18H18N6O4S2

305 Brown 3900(3931)

350(328)

1530(1529)

2100(2136) mdash 54952 Loss of NH2

4 [Co(HAEP)(H2O)2]2Co2C18H26N4O8S2

295 Brown 3570(3589)

430(432)

930(930)

2000(1958) mdash 60186 Loss of NH2 and 4H

5 [Fe(HAEP)(H2O)Cl]2Fe2C16H22N4O6Cl2S2

300 Green 3050(3088)

351(354)

891(901)

1800(1797)

1100(1142) 62170 Loss of 2N 2C add 05H2O

6 [Cr(HAEP)(H2O)Cl]2Cr2C18H22N4O6Cl2S2

265 Green 3500(3523)

421(359)

900(913)

1550(1696)

1025(1158) 61312 Loss of NH2

7 [VO(HAEP)(H2O)2]VC9H13N2O5S

310 Grey 3450(3462)

320(417)

899(897)

1574(1633) 31200 Loss of NH2


Table 4 Elemental composition and physical data of BFH ligand and its complexes

S number Complex MPt∘C Colour C H N M Cl Mol Wt


1 BFH-L4(C12H10N2O2)

182 Yellow 6750(6763)

500(469)


2[Cr(BFH)(H2O)Cl2]2Cr2C24H20N4O6Cl4

pH 55ndash70270 Brown 4200

(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O

3[Cr(BFH)2(H2O)]Cl2CrC24H20N4O5Cl

pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O

4 [VO(BFH)2(H2O)]VC24H18N4O6

300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O

Table 5 Elemental composition and physical data of BHDH ligand and its complexes

S number Complex MPt∘C Colour C H N M Cl Mo Wt


1 BHDH-L5(C15H14N2O5)

240 Yellow 6000(6002)

500(466)


2 [Cr(BHDH)Cl]2Cr2C30H24N4O10Cl2

300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H

3 [VO(BHDH)(H2O)]VC15H14N2O7

305 Green 4055(4063)

390(391)

730(729)

1312(1327) mdash 38394 Loss of 2H 2C add H2O 4H

as 200mL into 10 (500mL) conical flasks containing 2 g ofagar-agar each All were inoculated and incubated A setof plates with a standard bactericide 2-bromo-2-nitro-1 3-propanediol (Bronidiol) for comparison and another set ofcontrol plates with distilled water were kept for evaluation ofresults All the data are consolidated in Table 20

3 Results and Discussion

Five new ligands were synthesized by mixing the appro-priate amine and the aldehyde condensation via a Schiffbase reaction (Scheme 1) All of the SBs thus formed arecrystalline powders white or pale-yellow in colour and arestable to air and moisture They are found to be soluble inmost of the polar solvents like ethanol methanol acetoneand so forth and also in bases All of themwere characterizedby elemental analyses melting points (Tables 1ndash6) and IRspectra (Tables 7ndash12) The elemental analyses of the ligandsshow that there is a loss of a few molecules during theCHN analyses probably due to the low melting points of thesynthesized ligands and the details are given in the remarkscolumn of the Tables 1ndash6 while the IR spectra show all theexpected structural peaks From the IR data in Table 7 it wasanalyzed that L1 acts as a tridentate ligand by coordinatingthrough ndashO of the deprotonated phenolic group ndashO ofanother deprotonated ndashOH group formed due to enolizationand ndashN of the azomethine group Table 8 shows that theL2 acts as a tridentate ligand similar to L1 and the ndashOHgroups of the resacetophenone moiety do not participate incoordination Table 9 gives the data for L3 which enolizes andacts as a tridentate ligand coordinating through the ndashO ofthe deprotonated phenolic group ndashS of the ndashSH group after

deprotonation and ndashN of the azomethine group Thus it isfound to remain in the ldquothionerdquo form and not in the ldquothiolrdquoform [65 66] in the solid state Table 10 gives details on L4acting as a bidentate ligand with ndashO and ndashN donors Table 11shows the details of L5 acting as a tetradentate bound throughthree ndashOrsquos and one ndashN and L6 not a Schiff base but useddirectly for complexation binds through carbonyl ndashO atomand ndashO of phenolic group as is shown in Table 12

They were used to make complexes with Cu(II) Ni(II)Co(II) Fe(III) Mn(II) Cr(III) and VO(II) metal ions Gen-erally all the metal complexes were synthesized in alcoholicsolutions at room temperature or by reflux at pH 55 or85 These were characterized by the usual analytical andspectroscopic methods All the complexes formed with therespective ligands have been shown to coordinate with thedenticity mentioned above and the shift of the coordinatingatoms is also shown in Tables 7ndash12 thus confirming theformation of stable metal chelates with the new Schiff basesand DHA L6 The physical data elemental analyses arealso given in Tables 1ndash6 for all the complexes synthesizedThese data for all the complexes also show a loss of a fewmolecules during the analysis of CHN probably due to thelower decomposition temperature while the IR spectra showall the expected structural peaks Some of the complexes haveone two or four coordinated water molecules which wereanalysed by TGA analyses The variable temperature data ofthese complexes from room temperature to decompositionof the complex and the loss in weight of the material takenconfirm the percentage of coordinated water which is presentin the complex composition predicted

The chemistry of ligands upon binding to different metalatoms leads to the formation of expected four andor sixcoordinate complexes and the salient features are discussed


Table 6 Elemental composition and physical data of DHA ligand and its complexes

S number Complex MPt∘C Colour C H M Mol Wt


1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash

2 [Cr(DHA)3]CrC24H24O12

285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O

3 [VO(DHA)2(H2O)]VC16H18O10

305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)

Figure 1 Electronic (MULL) spectra of OXOVANADIUM(N)complexes of (a) BHFH-[Vo(BHFH)(C1)]

2 (b) BHEH-[Vo(BHDH)

(C1)]2 (c) DHA-[Vo(DHA)

2(H2O)]

below based on the collected electronic and magnetic dataThe data are presented in Tables 13ndash19 and Figures 1ndash8 fordifferent metal ions

31 VO(II) Complexes All the OXOVANADIUM complexesare highly coloured fine amorphous powdersThey are stableto air moisture and insoluble in water and other commonorganic polar and nonpolar solvents They all decomposeabove 300∘C (except complex of L1 at 285∘C) V complex withL4 showed loss of weight starting at 52∘C (00006 gm) anddecomposed at 300∘C (00090 gm) complex with L3 at 50∘C(00004 gm) and decomposed at 310∘C (00088 gm) complexwith L5 at 50∘C (00008 gm) and decomposed at 305∘C(00096 gm) and complex with L6 at 50∘C (00009 gm) anddecomposed at 305∘C (00099 gm) in the thermal analysisthus confirming one or two molecules of water coordinationin the complexes as per the composition predicted

All the VO(II) complexes are paramagnetic as shownin Table 13 Figures 1 and 2 The values of L6 L3 and L5based complexes are in agreement with the expected spin-only value of 173 BM at RT However the complexes withL1 and L2 have shown lower values 15-16 BM may be due tolow symmetry expected at 173 BM when the orbital angularcontribution is almost quenched [67] and may occur due to

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)

Figure 2 Electronic (MULL) spectra ofOXOVANADIUM(II) com-plexes of (a) BHDH-[Vo(BHDH)(H

2O)] (b) HAEP-[Vo(HAEP)

(H2O)2] (c) BFH-[Vo(BFH)

2(H2O)]

the presence of exchange coupled antiferromagnetism [68]Several reports indicate such behavior [69ndash71] Hence theyare assigned binuclear structures

Electronic spectra show three bands below 30000 cmminus1at RT in diffuse reflectance mull data as given in Table 13corresponding to octahedral symmetry (Oh) with tetragonaldistortion The bands transitions molecular structure andthe predicted geometry are given inTable 13 A few complexesmay also show a vibrational structure with a spacing of700 cmminus1 at the 2B2 rarr 2E transition band correspondingto the V=O stretching frequency in the excited state which isnot clearly observed

32 Cr(III) Complexes All the Cr(III) complexes arecoloured solids and they are stable to air and moisture Theyare insoluble in water and in most of the common organicsolvents like methanol ethanol benzene acetone and soforth Hence conductivity could not be measured due to theinsolubility Cr complex with L4 at lower pH showed lossof weight starting at 110∘C (00005 gm) and decomposed at270∘C (00091 gm) complex with L4 at higher pH at 52∘C(00005 gm) and decomposed at 310∘C (00091 gm) andcomplex with L3 at 52∘C (00005 gm) and decomposed at265∘C (00091 gm) in the thermal analysis Thus confirming


Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex

IRcmminus1(s=sharpb=broadd=do

ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020

(s)895(s)cmminus1indicatesn

oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]


Table 8 Characteristic IR data for the L2-BHEH (tridentate ndashO ndashO and ndashN) and its participation in complex formation with metal ions

S number Complex IR cmminus1 (s = sharp b = broad d = doublet w = weak vw = very weak)Coord water vOndashHc vNndashHc vC=Od vC=Nd vC=O phenolice MndashO or MndashN or MndashClf

1 BHEH-L2g mdash 3330 (b)a 3260 (b)b 1650 (s) 1610 (s) 1240 (s) mdash2 [Cu(BHEH)Cl] mdash 3460 (b) 3340 (b) 1600 (s) 1585 (s) 1255 (s) 690 510 2703 [Ni(BHEH)2] mdash 3600 (b) 3340 (b) 1620 (s) 1600 (s) 1255 (s) 500 3804 [Co(BHEH)2] mdash 3450 (b) 3280 (s) 1620 (s) 1600 (s) 1255 (s) 650ndash4005 [Fe(BHEH)(H2O)Cl]2 3500ndash3450 (b) mdash 3340 (b) 1605 (s) 1580 (s) 1255 (s) 840 (s) 620 580 4906 [Mn(BHEH)2] mdash 3460 (b) 3280 (s) 1620 (d) 1600 (s) 1255 (s) 650ndash4007 [VO(BHEH)Cl]2 mdash 3500 (w) 3260 (b) 1600 (s) 1590 (s) 1260 (s) 970 (V=O) 570 520 340aIntramolecular hydrogen bonding bHydrogen bonding cShift indicates cleavage of intramolecular H bonds after complex formation dInvolvement of O ofcarbonyl group and N of azomethine group in complex formation Watt and Dowes [95] Truter and Rutherford [96] Cotton and Wilkinson [97] eDavisonand Christie [98] Kubo et al [99] indicates deprotonation of phenolic OH and binding to M fNakamoto [91 100] and Selbin [94] gNo change in vNndashN at1040 (w) cmminus1

300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)

Figure 3 Electronic (MULL) spectra of CHROMIUM(III) com-plexes of (a) DHA-[Cr(DHA)

3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)

HAEP-[Cr(HAEP)(C1)(H2O)]2 (d) BHDH-[Cr(BHDH)(C1)]

2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)

Figure 4 Electronic (MULL) spectra of MANGANESE(II) com-plexes of (a) BHFH-[Mn(BHFH)(C1)(H

2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

Figure 5 Electronic (MULL) spectra of IRON(III) complex of (a)BHFH-[Fe(BHFH)(C1)

2]2 (b) BHEH-[Fe(BHEH)(C1)(H

2O)]2 (c)

HAEP-[Fe(HAEP)(C1)(H2O)2]2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)

Figure 6 Electronic (MULL) spectra of COBALT(II) complexesof (a) BHFH [Co(BHFH)(C1)(H

2O)]2 (b) HAEP [Co(HAEP)

(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno

tldquothiolrdquoform

inthesolid

stateas

theexpected

vSndashH

band

at2570

(s)cmminus1forldquothiolrdquoform

isno

tobservedandvC

=SispresentPradhanandRa

o[65]SahaandDeepak

[66]

andotherreferencesthereinSuzuk

i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu

etoenolizationandshift

inoriginalvC

=Ngrou

pof

azom

ethine


Table 10 Characteristic IR data for the L4-BFH (bidentate ndashO ndashN) and its participation in complex formation with metal ions

S number Complex IR cmminus1 (s = sharp b = broad d = doublet w = weak vw = very weak)Coord water vNndashH vC=O vC=Nd MndashO MndashN MndashCle

1 BFH-L4b mdash 3240 (s)a 1650 (s) 1620 (s) mdash2 [Cr(BFH)(H2O)Cl2]2 3550ndash3450 Absentc mdash 1610 (s) 1590 (s) 830 570 400 (s) 300 (vw)3 [Cr(BFH)2(H2O)Cl] 3550ndash3450 Absentc mdash 1610 (s) 1590 (s) 840 575 395 (s) 300 (vw)4 [VO(BFH)2(H2O)] 3550ndash3450 (b) Absentc mdash 1600ndash1610 (s) 970 (V=O) 810 440 350aHydrazone moiety bNo shift in symmetric and asymmetric stretching frequencies of furfural ring oxygen at 1020 (s) 895 (s) cmminus1 and NndashN at 1040 (w)indicates no involvement in complex formation cAbsence of vNndashH band suggests enolization of the ligand which is confirmed by disappearance of strongvC=O band dShift indicates participation of ndashN of azomethine group in coordination eNakamoto [91 100] and Selbin [94]

Table 11 Characteristic IR data for the L5-BHDH (tetradentate ndashO ndashO ndashN and ndashO) and its participation in complex formation with metalions

S number Complex IR cmminus1 (s = sharp b = broad d = doublet w = weak vw = very weak)Coord water vOndashH vNndashH vC=O vC=N vCndashO phenolic MndashO MndashN or MndashCl

1 BHDH-L5c mdash 3350ndash3400 (b)a 3280 (s) 1655 (s) 1600 (s) 1260 (s) mdash2 [Cr(BHDH)Cl]2 mdash Absentb 3280 (s) 1635 (s) 1580 (s) 1300ndash1310 (d) 550 (w) 435 310 295 (w)

3 [VO(BHDH)(H2O)] 3500ndash3450 (b) Absentb 3280 (s) 1610 (s) 1575 (s) 1270 (s) 970 (V=O) 820 (s) 520470 440 340

aInter and intramolecular hydrogen bonding bThe breakage of hydrogen bonding and the deprotonation of both the hydroxyl groups (phenolic) thatis hydrazide ndashOH and pyrone ndashOH and their MndashO coordination cNo shift of lactone vC=O at 1710 (s) cmminus1 and vCndashOndashC at 1010 (s) cmminus1 suggestsnoninvolvement in complex formation shift of hydrazide phenolic vCndashO and vC=N indicate participation in complexation

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)

Figure 7 Electronic (MULL) spectra of NICKEL(II) complexesof (a) BHFH (AT ph 85) [Ni(BHFH)]

2 (b) BHFH (AT ph

55ndash70) [Ni(BHFH)(H2O)] (c) BHEH [Ni(BHEH)

2] (d) HAEP

[Ni(HAEP)]2

one or two molecules of water coordination in the complexesas per the composition predicted

The Cr(III) complexes are synthesized with L3 L4 L5and L6 and are characterized [72 73] as having Oh geometryas shown in Table 14 Figure 3 The magnetic moments of L6and L4 (prepared at pH 85) at RT are close to the expectedspin-only value for Oh complexes of Cr(III) [72ndash75] Theother complexes show lower values and so may be due tometal-metal interactions with binuclear bridge structures Allthe electronic spectra for several greenish Cr(III) complexes

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

Figure 8 Electronic (MULL) spectra of Copper(II) complexesof (a) BHFH (AT ph 55ndash70)-[Cu(BHFH)]

2 (b) BHFH (AT ph

85)-[Cu(BHFH)(H2O)] (c) BHEH-[Cu(BHEH)(C1)] (d) HAEP-

[Cu(HAEP)]2

fit with very large number of such complexes studied andsurveyed However in the present case the highest energyband is found to be obscured due to the dark colour of allthe complexes

33 Mn(II) Complexes The Mn(II) complex of L1 is a finepowder light-yellow in colour and decomposed at 280∘Cwithout melting The Mn(II) complex of L2 is a dark-brownpowder decomposed at 286∘C Both the compounds are verystable in air and moisture and are insoluble in water and


Table 12 Characteristic IR data for the ligand DHA (bidentate ndashO ndashO) and its participation in complex formation with metal ions

S number Complex IR cmminus1 (s = sharp b = broad d = doublet w = weak vw = very weak)Coord water vOndashH vC=O (lactone) vC=O vCndashO phenolic MndashO

1 DHA-L6b mdash 3030 (s)a 1710 (s) 1655 (s) 1265 (s) mdash2 [Cr(DHA)3] mdash Absentc 1740 (s) 1635 (s) 1280 (s) 480 4403 [VO(DHA)2(H2O)] 3500ndash3400 (b) Absentc 1740 (s) 1640 (s) 1290 (s) 910 (V=O)d 850 480 440aIntramolecular hydrogen bonded bNo shift in vCndashOndashC indicates noninvolvement in complex formation Mahesh and Gupta [103] cCleavage of hydrogenbonding due to complexation dSelbin [94]

in common organic solvents like methanol ethanol chloro-form benzene and so forth Mn complex with L1 at lowerpH showed loss of weight starting at 56∘C (00014 gm) anddecomposed at 280∘C (00205 gm) in the thermal analysisthus confirming a molecule of water coordination in thecomplex as per the composition predicted

As can be seen from Table 15 Figure 4 Mn(II) complexof L1 shows subnormal magnetic moment which may bedue to metal-metal interactions or due to spin-exchange orsuperexchange in the solid state [76 77]TheMn(II) complexof L2 is 592 BM expected region for high-spin Oh Mn(II)complexes [72 73]The electronic spectra are consistent withthe Oh symmetry in both the cases

34 Fe(III) Complexes All the complexes are dark colouredand fine amorphous powders All decomposed above 300∘Care very stable to air moisture and insoluble in most of thecommon organic solvents like acetone methanol ethanoland so forth They are soluble to some extent in solventslike 1-4 dioxane dimethylformamide and dimethyl sulfoxideTheir conductivity could not be measured owing to theirinsoluble nature Fe complex with L2 showed loss of weightstarting at 68∘C (00012 gm) and decomposed at 305∘C(00057 gm) and complex with L3 at 66∘C (00018 gm) anddecomposed at 300∘C (00055 gm) in the thermal analysisThus confirming two molecules of water coordination in thecomplexes as per the composition predicted

All the Fe(III) complexes formed with L1ndashL3 ligands havesubnormal magnetic moments which may be due to the factthat metal-metal interactions or superexchange is anticipated[76 78 79] as all the complexes may be binuclear in natureas shown in Table 16 Figure 5 The electronic spectra havevery weak transitions and could not be concluded decisivelyand however are close toOh symmetry with some tetragonaldistortion

35 Co Complexes All Co(II) complexes are coloured fineamorphous powders and decompose above 260∘C withoutmeltingThey are all very stable to air moisture and insolublein most of the common organic solvents and to a smallextent in 1-4 dioxane dimethylformamide and dimethylsulfoxide The conductivity of the compounds could not bedetermined owing to their insoluble nature Co complexwith L1 showed loss of weight starting at 52∘C (00020 gm)and decomposed at 260∘C (00555 gm) and complex with L3at 54∘C (00007 gm) and decomposed at 295∘C (00089 gm)in the thermal analysis thus confirming two molecules of

water coordination in the complexes as per the compositionpredicted

The observed magnetic moments of all the three Co(II)complexes formed with L1ndashL3 ligands are slightly lower thanthe expected 47ndash52 BM for high-spin octahedral Co(II)complexes as given in Table 17 Figure 6 The lower momentsmay be due to the metal-metal interactions [80]

In the Oh Co(II) complexes 4T1g and Eg are the spin-free and spin-paired ground states Broad band in lowerenergies and a multiple band in slightly higher energy inadmixtures with spin-forbidden transition to doublet stateare expected [72] The asymmetric visible band is typical ofOh Co(II) complexes the shoulder on the high energy sidebeing assigned to spin-forbidden transitions [74]

36Ni(II) Complexes Ni(II) complexes are bright-red greenand dark-brown in colour These are insoluble in water andsparingly soluble in common organic solvents and also in1-4 dioxane dimethylformamide and dimethyl sulfoxideThe conductivity could not be measured owing to very lowsolubility of the complexes Ni complex with L1 at lowerpH showed loss of weight starting at 68∘C (00010 gm) anddecomposed at 265∘C (00053 gm) in the thermal analysisthus confirming a molecule of water coordination in thecomplex as per the composition predicted

The L1 complex at pH 55ndash70 and the L3 complexes arediamagnetic [81] and the other two with L1 at pH 85 andL2 have magnetic moment around 291ndash340 BM as expectedfor six-coordinated spin-free Ni(II) complexes as seen inTable 18 Figure 7 In regular Oh complexes of Ni(II) con-sideration of spin-orbit coupling and contribution from the3A2g and the next higher 3T2g states give a somewhat highermagnetic moment than the spin-only moment of 283 BM[72 82 83]

The electronic spectra of the diamagnetic complex withL1 at pH 55ndash70 show two bands assigned to strongcharge-transfer d-pilowast transition [84] and the lower energyband to 1A1g rarr 1A2g transition [74 84ndash87] as expectedfor square-planar complexes The other two complexesshow three intense bands expected for regular octahedralgeometry

37 Cu(II) Complexes All the complexes are coloured fineamorphous powders and decompose above 250∘C withoutmelting They are all very stable to air moisture and areinsoluble in most of the common organic solvents exceptto a small extent in 1-4 dioxane dimethylformamide anddimethyl sulfoxide The conductivity could not be measured


Table 13 Electronic spectra and magnetic moment data for VO(II) complexes with L1ndashL6 ligands predicted molecular formula structureand geometry

S number Molecular formula-electronic spectrab bands transitionsapredicted structure (a rough MndashL sketch given) and geometrya 120583eff BM

1

[VO(BHFH)Cl]2MndashM complex with Cl bridgesV=O and two L1 with ndashO ndashO

and ndashN coordination

280061827013330

2B2-2A12B2-2B12B2-2ECorrespond to Ohsymmetry withtetragonal distortion

O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2

[VO(BHEH)Cl]2MndashM complex with Cl bridgesV=O and two L2 with ndashO ndashO


250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3

[VO(HAEP)(H2O)2]Distorted Oh complex V=O twondashOH2 and L3 with ndashN ndashO and

ndashS coordination on theequatorial plane

250002220013560

NO

O

S

OH2

OH2

V2minus 172

4

[VO(BFH)2(H2O)]Distorted Oh complex V=OndashOH2 and two L4 with ndashN ndashO

coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5

[VO(BHDH)(H2O)]Distorted Oh complex V=O

ndashOH2 and L5 with ndashN ndashO ndashOand ndashO coordination on the

equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6

[VO(DHA)2(H2O)]Distorted Oh complex V=OndashOH2 and two L6 with ndashO ndashOcoordination on the equatorial

plane

300002550018180

O

OO

O OOH2

V2minus 172

aLever [73] Rana et al [104] bRecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigures 1 and 2

owing to their insoluble nature and their stoichiometryis deduced from the analytical data and geometry fromthe diffuse reflectance data in conjunction with magneticmoments Cu complex with L1 at higher pH showed lossof weight starting at 73∘C (00010 gm) and decomposed at

280∘C (00300 gm) in the thermal analysis thus confirminga molecule of water coordination in the complex as per thecomposition predicted

The subnormal magnetic moments of Cu L1 at lower pHandCu L3 indicate somemetal-metal interactions in the solid


Table 14 Predicted molecular formula structure and geometry from electronic spectra and magnetic moment data for Cr(III) complexeswith L3ndashL6 ligands


1

[Cr(HAEP)(H2O)Cl]2Distorted Oh complex with Clbridges two ndashOH2 and two L3

with ndashO ndashN and ndashScoordination on the equatorial

plane

2793017390

4A2g-4T1g (F)4A2g-4T2gCharge transfertransition4A2g-4T1g (P) isobscured due to darkcolourOctahedral symmetryhigh-spin complex

Cl

Cl N

N

O

OS

SOH2

OH2

CrminusCrminus349MndashM

2

[Cr(BFH)(H2O)Cl2]2Distorted Oh complex with Clbridges two ndashCl two ndashOH2 andtwo L3 with ndashO ndashN coordination

on the equatorial plane

2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3

[Cr(BFH)2(H2O)Cl]Distorted Oh complex with

ndashOH2 Cl and two L3 with ndashOndashN coordination on the

equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4

[Cr(BHDH)Cl]2Distorted Oh complex with Clbridges and two L5 with ndashO ndashNndashO and ndashO coordination on the

equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]

Distorted Oh complex with threeL6 with ndashO ndashO coordination

2667018200 O

O

O

O

O

O

Crminus389

aLever [73] bRecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 3

state The dimeric nature of the complexes predicted with ndashO and ndashS as bridges supports this [88 89] All the data inthe references cited show that magnetic moments of square-planar Cu(II) complexes lie in the range of 17ndash19 BMWhileslightly higher values of the other two complexes suggestpresence of one unpaired electron with spin-orbit coupling[90] Thus all of the Cu(II) complexes are assigned [72]square-planar geometry as shown in Table 19 Figure 8 Twoof them indicate metal-metal interactions due to slightlylower magnetic moments one of them shows a loss of weight

corresponding to one molecule of water from the TGAat variable temperature and one another with the chlorideestimation

38 Physiological Activity The effect of themetal complex onfungal growth is measured by poisoning the nutrient (a solidlike an agar-agar or a liquid medium) with a fungi toxicantThen it is allowed to grow as a test fungus


Table 15 Predicted molecular formula structure and geometry from electronic spectra and magnetic moment data for Mn(II) complexeswith L1-L2 ligands


1

[Mn(BHFH)(H2O)Cl]2Distorted Oh complex with Clbridges two ndashOH2 and two L1

with ndashO ndashO and ndashNcoordination on the equatorial

plane

27030212701961018180 6A1g-4Eg 4A1g (G)

6A1g sdot 4T2g (G)6A1g sdot T1g (G)

Oh high-spin geometryis predicted

MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]

Oh complex with two L2 withndashO ndashO and ndashN coordination

2667017240 O

NH

O

O

O

NH

Mnminus 592

aPappalardo [105] brecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 4

Table 16 Predicted molecular formula structure and geometry from electronic spectra and magnetic moment data for Fe(III) complexeswith L1ndashL3


1

[Fe(BHFH)Cl2]2Distorted Oh complex with Cl bridges two ndashCland two L1 with ndashO ndashO and ndashN coordination on

the equatorial plane

23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2

[Fe(BHEH)(H2O)Cl]2Distorted Oh complex with Cl bridges twondashOH2 and two L2 with ndashO ndashO and ndashNcoordination on the equatorial plane

2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3

[Fe(HAEP)(H2O)Cl]2Distorted Oh complex with S bridges two ndashOH2two ndashCl and two L3 with ndashO ndashN and ndashS (used inbridging) coordination on the equatorial plane

Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM

aOh geometry with metal-metal interactions bRecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 5

39 For the Organism Rhizoctonia Solani

(i) L1 has shown 30 inhibition at 1000 ppm 17 at500 ppm and nil effect at 250 ppm (Table 20) Henceall the newly synthesized complexes were tested foractivity at 1000 ppm (observe carefully Figure 9) Itwas found that the VO(II) complex is 100 effective

Mn(II) 95 Fe(III) 62 Co(II) nil effect Ni(II) 45and Cu(II) nil effect Thus the activity order may beevaluated as VO gtMn gt Fe gt Ni gt L1 gt Co = Cu

(ii) L2 shows the following trend VO gtMn gt Ni gt Cu gtL2 gt Co


Table 17 Predicted molecular formula structure and geometry from electronic spectra and magnetic moment data for Co(II) complexeswith L1ndashL3 ligands


1

[Co(BHFH)(H2O)Cl]2Distorted Oh complex with Cl

bridges two minusOH2 and two L1 withndashO ndashO and ndashN coordination on


31250200001852015400

4T1g (F)-4T1g (P)4T1g (F)-4T2g (F) broadbandsMultiple bands inadmixture withspin-forbiddentransition to doubletstate

CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2

[Co(BHEH)2]Oh complex with two L2 with ndashOndashO and ndashN coordination on the

equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3

[Co(HAEP)(H2O)2]2Distorted Oh complex with S

bridges two ndashOH2 two ndashCl andtwo L3 with ndashO ndashN andndashS (used in

bridging) coordination on theequatorial plane

2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O

CominusCominus 453MndashM

aLever [73] the asymmetric visible band is typical ofOhCo(II) complexes and the shoulder on the high energy side being assigned to spin-forbidden transitionsDrago [74] bRecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 6

Figure 9 Activity observed for the following 1mdashDithane M45-500 ppm 2mdashVO(II)-250 ppm 3mdashVO(II)-500 ppm 4mdashVO(II)-750 ppm 5mdashVO(II)-1000 ppm and 6mdashBlank

(iii) quite unexpectedly L3 upon complexation com-pletely subsides the activity This may be due to thepresence of two free ndashOH groups and one free ndashNH2group in the ligand the structure of which is

comparable to the antidotes used for the expulsion offood poisoning in hospitals

Figure 10 Complexes with VO(II)-100 effective Mn(II)-95effective Fe(III)-62 effective Ni(II)-45 effective and Co(II)Cu(II)-nil effect are observed in this photo

(iv) L4 trend shows VO gt Cr gt L4(v) L5 L6 show VO gt Cr

Thus the complexes with L1 L2 and L4 are as effectiveas the commercially used Dithane M-45 (Table 20) The VOcomplexes with L1 and L2 are dimeric in nature and probablyin solution dissociate to monomeric units due to the V=O


Table 18 Predicted molecular formula structure and geometry from electronic spectra and magnetic moment data for Ni(II) complexeswith L1ndashL3 ligands


1

[Ni(BHFH)H2O]Square-planar complex with ndashOH2

and L1 with ndashO ndashO and ndashNcoordination on the equatorial

plane

2613018100

Charge-transfer band d-pilowasttransition1A1g sdot 1A2g

Square-planar geometry

O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]

Regular Oh complex with two L1with ndashO ndashO and ndashN coordination

2630015000

9520 (w)

3A2g-3T1g (P)3A2g-3T1g (G)3A2g-3T2g

Regular Oh geometry O

O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)

Strong charge-transferband-d-pilowast transition

3A2g-3T1g (P)3A2g-2T1g 3T1g (F)

3A2g-3T2gRegular Oh geometry

O

O N

N

O

O

Niminus 291

4

[Ni(HAEP)2]Distorted square-planar complexwith S bridges and two L3 with ndashO

ndashN ndashS (used in bridging)coordination on the equatorial

plane

2703016600

Charge-transfer band d-pilowasttransition1A1g-1A2g

Diamagnetic tetragonal orsquare planar complex with

high intensity band in14000ndash18000 cmminus1

Ni

N

O

S

NiN

O

S

DiaMndashM

aHolm et al [77] Shaw and Dudek [106] Drago [74] bRecorded for solid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 7

group unlike the other dimeric complexes synthesized ThendashO of V=O might bind in such a way that the activityorder is tremendously increased and the growth of fungus iscompletely inhibited making it 100 effective And probablythe ligands are bound to metal atoms by rearrangementcaused by enolization thus making them more viable fordissociation unlike the first deceptive appearance they giveas if they are coordinately more saturated

In the Case of Acrocylindrium oryzae a nominal activityfor the L4ndashL6 Cr(III) complexes and maximum activity forall VO(II) complexes were observed Hence screening ofVO(II) complex of L1 was done at lower concentrations andcompared with the commercially used fungicide DithaneM-45 (observe carefully Figure 10) From the average offour replications in each case the dry-weight of the fungal

mycelium was recorded in milligrams and was shown inTable 20 It was observed that L1ndashL3 has totally inhibitedthe growth at 1000 500 and 250 ppm Nominal growth ofthe organism on the disc of the inoculums was observedto be about 2ndash5mg but L4 showed nominal activity at1000 ppm with decreased activity at lower concentrations Sothe activity order for all these is given as follows L1 gt VO gtNi gt Mn gt Fe gt Co gt Cu and L2 gt Ni gt VO gt Mn gt Fe gtCu gt Co Cr(III) complexes of L3ndashL6 were found less toxicthan VO(II) complexes The activity of these was found to bemarginal when compared to that of the commercial DithaneM-45 Interestingly it was found that the VO(II) complexat 250 ppm is more effective compared to Dithane M-45 at500 ppmandmay bemore useful It is interesting to note fromthe above data that L1 and L2 are very toxic to this organism


Table 19 Predictedmolecular formula structure and geometry from electronic andmagnetic moment data for Cu(II) complexes with L1ndashL3ligands


1

[Cu(BHFH)]2 Distortedsquare-planar complex with MndashMcomplex with ndashO of L1 bridges and

L1 with the rest of ndashO ndashNcoordination

28570 (sm)14300 (b)

Strongcharge-transferband d-pilowasttransition2B2g-Eg2B2g-2A1g2B2g-2B1gNormally Cu(II)show broad bandsaround16670ndash1110 cmminus1The observedspectra resembleCu(II)-SBcomplexes whosegeometry isconsidered squareplanar

O

NO

O

ON

Cuminus

Cuminus

150MndashM

2

[Cu(BHFH)H2O]Distorted square-planar complex

with ndashOH2 and L1 with ndashO ndashO andndashN coordination

27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3

[Cu(BHEH)Cl]Distorted square-planar complexwith ndashCl and L1 with ndashO ndashO and

ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4

[Cu(HAEP)]2Distortedsquare-planar complex with S

bridges and two L3 with ndashO ndashNand ndashS (used in bridging)

coordination on the equatorialplane

256401538013330

S

S

ON

ONCuminus Cuminus 140

MndashM

aLever [73] Sutton [107] Satyanarayana and Mohapathra [108] Sacconi and Ciampolini [109] Muzundar and Bhattacharya [110] Sheela [111] bRecorded forsolid compounds (mull-diffuse reflectance) at room temperaturemdashFigure 8

compared to Rhizoctonia solani and also VO(II) complexesshow more activity

After 48 hrs of inoculation of the bacteriumXanthomonasoryzae percentage inhibition growth was calculated fromeach plate and average readings from fine replicas are shownin Table 20 It was observed that neither the ligands northe complexes could control the growth of this bacteriumfully None of the complexes showed considerable percentageinhibition at the 1000 ppm concentration and hence theywere not screened at lower concentrations The saturatedbactericide Branidiol was also found to be effective only tothe extent of 50 but its effect so persists in the system thatthe growth is arrested at that stage and never continues Theorder of activity of complexes of L1 is as follows VO gtMn gtFe gt L1 gt Ni gt Co gt Cu and that in the complexes of L2 is Ni

gt Mn gt VO gt Co gt Fe gt Cu gt L2 L3 and all its complexeshave shown nil activity on this bacterium L4ndashL6 and theirCr(III) VO(II) complexes were screened and the order ofactivity in themwas as follows VO gtCr gt L4 gt L5 gt L6Thusit was observed that the complexation increases the activity ofligand but it was less than the standard bactericide Bronidiol

4 Conclusions

Synthesis of Schiff bases L1ndashL5 and L6 and their use asligands for coordinationwithVO(II) Cr(III)Mn(II) Fe(III)Co(II) Ni(II) and Cu(II) form a major study All theprepared complexes were analyzed by C H N Cl andmetal analyses They were assigned molecular structures andgeometries using information obtained from IR UV-Vis


Table 20 Evaluation of fungicidal property of Schiff bases and metal complexes in vitro

S number Chemicalcomplex

Rhizoctonia solani (PDAmedium) average

inhibition of growth after 72 hrspoisoned food technique

Acrocylindrium oryzae (PAliquid) average

inhibition of growth after 48 hrsliquid broth method

Xanthomonas oryzae (Haywardrsquosmedium) average

inhibition of growth after 8 daysinhibition zone technique

concentration in ppm concentration in ppm concentration in ppm1000 500 250 1000 500 250 1000 500 250

1 BLANK - - - 246 245 246 - - -2 DITHANE-M-45 100 100 80 nil 200 240 55 50 483 L1-BHFH 30 1666 - nil nil 2 12 - - - -4 [Cu(BHFH)]2 - - - - - 190 200 240 5 - - - -5 [Co(BHFH)(H2O)Cl]2 - - - - - 170 150 240 8 - - - -6 [Ni(BHFH)]2 455 15 - 5 28 130 112 - - - -7 [Fe(BHFH)Cl2]2 622 344 10 55 100 220 223 - - - -8 [Mn(BHFH)(H2O)Cl]2 952 672 40 25 76 130 23 - - - -9 [VO(BHFH)Cl]2 100 6966 50 nil nil 12 20 - - - -10 L2-BHEH 20 66 - nil nil 2 3 - - - -11 [Cu(BHEH)Cl] 25 211 10 150 200 245 8 - - - -12 [Co(BHEH)2] - - - - - 175 190 225 167 - - - -13 [Ni(BHEH)2] 27 - - - - nil nil nil 30 - - - -14 [Fe(BHEH)(H2O)Cl)]2 35 20 - 100 155 200 15 - - - -15 [Mn(BHEH)2] 82 50 50 96 100 150 19 - - - -16 [VO(BHEH)Cl]2 100 45 40 nil nil 50 20 - - - -17 L3-HAEP 50 20 - 5 5 5 10 - - - -18 [Cu(HAEP)]2 - - - - - 245 - - - - - - - - - -19 [Co(HAEP)(H2O)2]2 - - - - - 240 - - - - - - - - - -20 [Ni(HAEP)2] - - - - - 185 - - - - - - - - - -21 [Fe(HAEP)(H2O)Cl]2 - - - - - 200 - - - - - - - - - -22 [Cr(HAEP)(H2O)Cl]2 - - - - - 242 - - - - - - - - - -23 [VO(HAEP)(H2O)2] - - - - - 245 - - - - 2 - - - -24 L4-BFH 32 20 - 70 100 240 20 - - - -25 [Cr(BFH)(H2O)Cl2]2 - - - - - 150 200 240 22 - - - -26 [VO(BFH)2(H2O)] 98 6966 50 125 150 200 25 - - - -27 [Cr(BHDH)Cl]2 155 512 5 190 - - - - 15 - - - -28 [VO(BHDH)(H2O)] 322 15 - 150 198 240 20 - - - -29 [Cr(DHA)3] 285 - - - - 200 240 245 15 - - - -30 [VO(DHA)2(H2O)] 50 30 15 170 200 238 18 - - - -- indicates negative effect - - indicates that the compound is not screened

magnetic susceptibility and TGA analysis The physiologicalactivity studies with ligands L1ndashL4 along with some results ofmetal complexes with L1ndashL6 ligands are tabulated suggestingthem to be toxic to the organisms studied and hence may beuseful as fungicides and bactericides The VO(II) complexesare found to be more active compared to the activity of thecommercial standard

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

The author T Mangamamba would like to thank All IndiaCoordinated Rice Improvement Project (ACRIP) Rajen-dranagar Hyderabad for allowing her to use their facility forthe study of physiological activity

References

[1] S Patai ldquoThe chemistry of carbon-nitrogen double bondrdquo inGeneral and Theoretical Aspects C Sandorfy Ed chapter 1pp 1ndash60 Interscience William Clowes and Sons London UK1970

[2] F P Dwyer and D P Mellor Chelating Agents and MetalChelates Academic Press New York NY USA 1964

[3] H Holm G W Everett and A Chakraborty ldquoMetal complexesof Schiff bases and 120573-ketoaminesrdquo Progress in Inorganic Chem-istry vol 7 pp 83ndash214 1966

[4] J W Smith The Chemistry of Carbon-Nitrogen Double Bondedited by S Patai International Science Publishing LondonUK 1970

[5] L F Lindoy ldquoMetal-ion control in the synthesis of Schiff basecomplexesrdquo Quarterly Reviews Chemical Society vol 25 no 3pp 379ndash391 1971

[6] B O West E A V Ebsworth A G Maddock and A G SharpNew Pathways in Inorganic Chemistry Cambridge UniversityPress London UK 1966


[7] S Yamada ldquoRecent aspects of the stereochemistry of Schiff-base-metal complexesrdquo Coordination Chemistry Reviews vol 14 pp 415ndash437 1966

[8] M J Norgett J H MThornley and L M Venanzi ldquoThe visibleand ultraviolet spectra of d6- d7- and d8-metal ions in trigonalbipyramidal complexesrdquo Coordination Chemistry Reviews vol2 no 1 pp 83ndash98 1967

[9] N F Curtis ldquoMacrocyclic coordination compounds formedby condensation of metal-amine complexes with aliphaticcarbonyl compoundsrdquo Coordination Chemistry Reviews vol 3no 1 pp 3ndash47 1968

[10] E Bayer ldquoStructure and specificity of organic chelating agentsrdquoAngewandte Chemie International Edition vol 3 no 5 pp 325ndash332 1964

[11] E Jungreis and SThabet ldquoAnalytical application of schiff basesrdquoin Chelates in Analytical Chemistry H A Flaschka and A JBarnard Jr Eds vol 2 pp 149ndash177 Marcel Dekker New YorkNY USA 1969

[12] F Feigl Spot Tests inOrganic Analysis vol 2 Elsevier NewYorkNY USA 1958

[13] J C Bailar Chemistry of Coordination Compounds Reinhold1956

[14] A E Martell and M Calwin Chemistry of Metal ChelateCompounds Prentice-Hall Upper Saddle River NJ USA 1952

[15] S Chaberek and A Martell Sequestering Agents John Wiley ampSons New York NY USA 1959

[16] R L SmithThe Sequesteration of MetalsTheoretical Considera-tions and Practical Applications Chapman ampHall London UK1959

[17] E R Inman and I A Macpherson ChemicalAbstracts vol 74Article ID 77398 1971

[18] C S Marvell and N Tarkoy ldquoHeat stability studies on chelatesfrom schiff bases of salicylaldehyde derivatives IIrdquo Journal ofthe American Chemical Society vol 80 no 4 pp 832ndash835 1958

[19] W Qin S Long M Panunzio and B Stefano ldquoSchiff bases ashort survey on an evergreen chemistry toolrdquoMolecules vol 18no 10 pp 12264ndash12289 2013

[20] S Kumar D N Dhar and P N Saxena ldquoApplications of metalcomplexes of Schiff basesmdasha reviewrdquo Journal of Scientific andIndustrial Research vol 68 no 3 pp 181ndash187 2009

[21] R Katwal H Kaura and B K Kapur ldquoApplications of coppermdashSchiff rsquos base complexes a reviewrdquo Scientific ReviewsampChemicalCommunications vol 3 no 1 pp 1ndash15 2013

[22] R K Parashar R C Sharma andGMohan ldquoBiological activityof some Schiff bases and theirmetal complexesrdquoBiological TraceElement Research vol 23 pp 145ndash150 1990

[23] S Pattanaik S S Rout J Panda P K Sahu and M Baner-jee ldquoSynthesis characterisation and biological evaluation ofbedentate ligands (Reduced Schiff rsquos Base)withmetals of coppernickel and zinc complexesrdquo Rasayan Journal of Chemistry vol4 no 1 pp 136ndash141 2011

[24] S Malik S Ghosh and L Mitu ldquoComplexes of some 3d-metalswith a Schiff base derived from 5-acetamido-l34-thiadiazole-2-sulphonamide and their biological activityrdquo Journal of theSerbian Chemical Society vol 76 no 10 pp 1387ndash1394 2011

[25] K Krishnankutty M B Ummathur and P Sayudevi ldquoMetalcomplexes of schiff bases derived from dicinnamoylmethaneand aromatic aminesrdquo The Journal of the Argentine ChemicalSociety vol 96 no 1-2 pp 13ndash21 2008

[26] P Subramanian and M Sakunthala ldquoAntibacterial activities ofnew Schiff base metal complexes synthesised from 2-hydroxy-1-naphthaldehyde and 5-amino-1-naphtholrdquo World Journal ofPharmacy and Pharmaceutical Sciences vol 2 no 5 pp 2753ndash2764 2013

[27] B Lakshmi K N Shivananda G A Prakash A M Isloor andK N Mahendra ldquoSynthesis and characterization of schiff basemetal complexes and reactivity studies with malemide epoxyresinrdquo Bulletin of the Korean Chemical Society vol 33 no 2 pp473ndash482 2012

[28] G Puthilibai Synthesis spectral electrochemical antibacterialand DNA binding properties of Cu(II) Ni(II) and Co(II)Schiff bases complexes derived from 2-HCl Br-4-HCl-6-(4-fluorophenlyiminomethyl)phenol [PhD thesis] 2010

[29] A Sharma T Mehta and M K Shah ldquoSynthesis and spectralstudies of transition metal complexes supported by NO- biden-tate Schiff-Base ligandrdquo Pelagia Research Library Der ChemicaSinica vol 4 no 1 pp 141ndash146 2013

[30] M B Halli R S Malipatil R B Sumathi and K ShivakumarldquoSynthesis spectroscopic characterization and biological activ-ity studies of Schiff base metal complexes derived from N1015840-(4-(methylthio) benzylidene)benzofuran-2-carbo hydraziderdquo DerPharmacia Lettre vol 5 no 4 pp 182ndash188 2013

[31] NAkbolat A YıldızH Temel S Ilhan andGGul ldquoAntifungalstudies of some metal complexes with Schiff base ligandsrdquoDUFED vol 1 no 1 pp 15ndash22 2012

[32] G G Mohamed M M Omar and A M Hindy ldquoMetalcomplexes of Schiff bases preparation characterizationandbiological activityrdquo Turkish Journal of Chemistry vol 30 no 3pp 361ndash382 2006

[33] E Yousif A Majeed K Al-Sammarrae N Salih J Salimonand B Abdullah ldquoMetal complexes of Schiff base preparationcharacterization and antibacterial activityrdquo Arabian Journal ofChemistry 2013

[34] V Arun and K K Mohammed Yusuff Synthesis and character-isation of new transition metal complexes of Schiff bases derivedfrom 3-hydroxyquinoxaline-2-carboxaldehyde and application ofsome of these complexes as hydrogenation and oxidation catalysts[PhD thesis] Cochin University 2009

[35] M A Neelakantan M Esakkiammal S S Mariappan JDharmaraja and T Jeyakumar ldquoSynthesis characterization andbiocidal activities of some schiff base metal complexesrdquo IndianJournal of Pharmaceutical Sciences vol 72 no 2 pp 216ndash2222010

[36] SMalik G Suparna J Bharti S Archana andM BhattacharyaldquoSynthesis characterization and biological evaluation of some3d-metal complexes of schiff Base derived fromxipamide drugrdquoInternational Journal of Inorganic Chemistry vol 2013 ArticleID 549805 6 pages 2013

[37] Z H Chohan A Munawar and C T Supuran ldquoTransitionmetal ion complexes of Schiff-bases Synthesis characterizationand antibacterial propertiesrdquo Metal-Based Drugs vol 8 no 3pp 137ndash143 2001

[38] R B Sumathi and M B Halli ldquoMetal (II) complexes derivedfrom naphthofuran-2-carbohydrazide and diacetylmonoximeSchiff base synthesis spectroscopic electrochemical and bio-logical investigationrdquo Bioinorganic Chemistry and Applicationsvol 2014 Article ID 942162 11 pages 2014

[39] O B Ibrahim M A Mohamed and M S Refat ldquoNano sizedschiff base complexes with Mn (II) Co(II) Cu(II) Ni(II) andZn(II) metals synthesis spectroscopic and medicinal studiesrdquoCanadian Chemical Transactions vol 2 no 2 pp 108ndash121 2014


[40] D Suryarao and M C Ganorkar ldquoPotential fungitoxicity ofsome transition-metal chelates derived fromdehydroacetic acidon Rhizoctonia-Solanirdquo National Academy Science Letters vol1 p 402 1978

[41] D Suryarao and M C Ganorkar ldquoSynthesis and physiological-activity of new schiff bases of dehydroacetic acid and theirmetalchelatesrdquo Current Science vol 49 p 511 1980

[42] D Suryarao and M C Ganorkar ldquoSynthesis and biologicalstudies of some metal complexes of benzaldehyde salicyloylhy-drazenerdquo Journal of the Indian Chemical Society vol 58 p 2171981

[43] W A Sexton Chemical Constitution and Biological Activity Eamp F N Span London UK 1963

[44] D Reddick and E Wallace ldquoOn a laboratory method of deter-mining the fungicidal value of a spray mixture on solutionrdquoScience vol 31 p 798 1910

[45] S E A Mc Callan ldquoStudies on fungicides II Testing protectivefungicides in the laboratoryrdquo Cornell University AgriculturalExperimental Station Manual vol 128 p 14 1930

[46] Committee on Standardization of Fungicidal Test The Ameri-can Phytopathological Society ldquoThe slide germination methodfor evaluating protectant fungicidesrdquo Phytopathology vol 33pp 627ndash632 1943

[47] Committee on Standardization of Fungicidal Test and TheAmerican Phytopathological Society ldquoThe glass slide germina-tion test by the test tube dilution method is adapted from aproducerdquo Phytopathology vol 33 pp 354ndash356 1947

[48] G R Mandels and R T Darby ldquoA rapid cell volume assay forfungitoxicity using fungus sporesrdquo Journal of Bacteriology vol65 no 1 pp 16ndash26 1953

[49] H H Thornberry ldquoA paper-disc plate method for quantitativeevaluation of funcgicides and bactericidesrdquo Phytopathology vol40 pp 419ndash420 1950

[50] E G Sharvelle The Nature and Uses of Modern FungicidesBurgess Publishing Company St Paul Minn USA 1960

[51] E G Sharvelle and E N Pellertier ldquoModified paper-discmethod for laboratory fungicidal bioassayrdquo Phytopathology vol46 p 26 1956

[52] T Mangamamba [Ph D thesis] Osmania University Hyder-abad India 1982

[53] VAgnihotrudu Rallis India Fertilizers and PesticidesDivisionP B No 168 Bangalore India pp 69ndash71 1973

[54] S H Ou Rice-diseases [PhD thesis] IRRI Laguna Phillip-pines 1979

[55] R S Singh Plant diseases G B Panta University of Agricultureand Technology Nainital India 1980

[56] W C Vincent Physiology of Fungi [PhD thesis] WesleyanUniversity Middletown Conn USA 1979

[57] B S Furniss A J Hannaford V Rogers P W G Smithand A R Tatchell Eds Vogelrsquos Text Book of Practical OrganicChemistry ELBS London UK 1978

[58] R Stolle ldquoAs per procedure benzol chloride and anhydroushydrazine were mixed to obtain the desired benzohydrazinecrystalsrdquo Journal fur Praktische Chemie vol 69 p 145 1904

[59] R Hisada H Minato and M Kobayashi ldquoAroyl arenesulfonylperoxides IV The mechanism of carboxy inversion of benzolp-toluenesulfonyl peroxiderdquo Bulletin of the Chemical Society ofJapan vol 45 no 9 pp 2816ndash2814 1972

[60] M Ito and K Yatugaku Chemical Abstracts vol 34 p 410 1962

[61] M Dexter and B Manor ldquoPolyolefin compositions stabi-lized against detertoration and copper lsquowires coated with saidcompositionsrdquo NY assignor to Geigy Chemical CorporationGreenburgh NY a corporation of Delaware Filed 1962 No176451 US patent office Patented 3110696 1963

[62] A I Vogel A Text Book of Quantitative Organic AnalysisLongman London UK 1976

[63] D R Gupta and R S Gupta Indian Chemical Society vol 42421 1965

[64] B S Furniss A J Hannaford V Rogers P W G Smith andA R Tatchell Eds Vogelrsquos Text Books of Practical InorganicChemistry ELBS London UK 1978

[65] B Pradhan and D V R Rao Journal of the IndianChemicalSociety vol 57 p 136 1977

[66] N Saha and B Deepak Journal of Indian Chemical Society vol58 p 13 1981

[67] P Ray ldquoComplex compounds of biguanides and guanylureaswith metallic elementsrdquo Chemical Reviews vol 61 no 4 pp313ndash359 1961

[68] U V Zelentsov ldquoMagnetic properties of oxovanadium(iv)complexesrdquo Russian Journal of Inorganic Chemistry vol 7 p670 1962

[69] C C Lee A Shyamal and L J Theriot ldquoOxovanadium(IV)complexes with tridentate ONS donor ligandsrdquo InorganicChemistry vol 10 no 8 pp 1669ndash1673 1971

[70] S N Poddar K Day J Haldar and S C Nathsarkar ldquoMagneticproperties of oxovanadium(IV) complexes of substituted N-(hydroxyalkyl) salicylideneiminesrdquo Journal of the Indian Chem-ical Society vol 47 p 743 1970

[71] Y Kuge and S Yamada ldquoSchiff base oxovanadium(IV) com-plexes with subnormal magnetic momentsrdquo Bulletin of theChemical Society of Japan vol 43 no 12 p 3972 1970

[72] F A Cotton and G Wilkinson Advanced Inorganic ChemistryWiley-Eastern New Delhi India 3rd edition 1976

[73] A B P Lever Inorganic Electronic Spectroscopy Elsevier Ams-terdam The Netherlands 1968

[74] R S Drago Physical Methods in Inorganic Chemistry vol 168Reinhold 1965

[75] G N Figgis and J Lewis Progress in Inorganic Chemistry vol 6International Scientific Publications New York NY USA 1964

[76] A Earnshaw and J Lewis ldquoMagnetic properties of somebinuclear complexesrdquo Journal of the Chemical Society pp 396ndash404 1961

[77] R H Holm G W Everett Jr and A Chakravorty ldquoMetal com-plexes of Schiff bases and 120573-ketoaminesrdquo Progress in InorganicChemistry vol 7 pp 83ndash214 1966

[78] K L Madhok and K P Srivatsav ldquoSynthesis and charac-terization of hexa hepta and octa-coordinated Nb(V) com-plexes of NN1015840-(dsubstituted)-formamidino-N1015840-(substituted)carbamides and thiocarbamidesrdquo Proceedings of the IndianAcademy of Sciences Chemical Sciences vol 92 no 6 pp 605ndash612 1983

[79] W M Reiff A W Baker Jr and N E Erickger ldquoBinuclearoxygen-bridged complexes of iron(III) New iron(III)-221015840210158401015840-terpyridine complexesrdquo Journal of the American Chemical Soci-ety vol 90 no 18 pp 4794ndash4800 1968

[80] R H Holm and J OrsquoConnor ldquoThe stereochemistry of bis-chelate metal(II) complexesrdquo Progress in Inorganic Chemistryvol 14 pp 241ndash401 1971

[81] B N Figgis Introducion to Ligand Field Theory chapter 10Interscience Publishers New York NY USA 1966


[82] G N Figgis and J Lewis in Progress in Inorganic Chemistryvol 6 International Scientific PublicationsNewYorkNYUSA1964

[83] K D Buttler K SMurray and BOWest ldquoMagnetic propertiesof some tridentate Schiff base manganese (II) complexesrdquoAustralian Journal of Chemistry vol 24 no 11 pp 2249ndash22561971

[84] C L Perry and J M Weber ldquo Complexes of pyrrole-derivativeligandsmdashIII some first transition series metal complexes ofbidentate ligandsrdquo Journal of Inorganic and Nuclear Chemistryvol 33 pp 1031ndash1039 1971

[85] J P Jesson S Trofimenko and D R Eaton ldquoSpectra andstructure of some transition metal poly(1-pyrazolyl) boratesrdquoJournal of the American Chemical Society vol 89 no 13 pp3148ndash3158 1967

[86] R H Holm ldquoStudies on Ni(II) complexes I Spectra of tricyclicSchiff base complexes of Ni(II) and Cu(II)rdquo Journal of theAmerican Chemical Society vol 82 no 21 pp 5632ndash5636 1960

[87] W K Musker and M S Hussain ldquoMedium-ring complexesIII Comparison of planar and pyramidal copper(II) and planarnickel(II) complexes containing seven- and eight-membered-ring diaminesrdquo Inorganic Chemistry vol 8 supplement 3 pp528ndash536 1969

[88] A Shyamal and K S Kale Indian Journal of Chemistry A vol16 pp 46ndash48 1978

[89] S G Kulkarni [PhD thesis] Department of Chemistry Marat-wada University Aurangabad India

[90] A Earnshaw Introduction to Magneto Chemistry AcademicPress New York NY USA 1969

[91] K Nakamoto IR Spectra of Inorganic and Coordination Com-pounds Wiley-Interscience New York NY USA 1972

[92] K Ueno and A E Martell ldquoInfrared study of metal chelates ofbisacetylacetoneethylenediimine and related compoundsrdquo TheJournal of Physical Chemistry vol 59 no 10 pp 998ndash1004 1955

[93] KUeno andA EMartell ldquoInfrared studies on synthetic oxygencarriersrdquo The Journal of Physical Chemistry vol 60 no 9 pp1270ndash1275 1956

[94] J Selbin ldquoOxovanadium(IV) complexesrdquo Coordination Chem-istry Reviews vol 1 no 3 pp 293ndash314 1966

[95] G W Watt and J W Dowes ldquoCopper(0) phthalocyaninerdquoJournal of Inorganic and Nuclear Chemistry vol 14 no 1-2 pp32ndash34 1960

[96] M R Truter and KW Rutherford ldquo333The cystal structure oftetrakisthioacetamidecopper(I) chloriderdquo Journal of the Chem-ical Society pp 1748ndash1756 1962

[97] F A Cotton and G Wilkinson Advanced Inorganic ChemistryWiley-Eastern New York NY USA 3rd edition 1972

[98] W H T Davison and P E Christie ldquoInfrared spectra ofsemicarbazonesrdquo Journal of the Chemical Society pp 3389ndash33911955

[99] M Kubo M Kuroda M Krishita and Y Muto ldquo The structureof three-coordinated copper(II) complexes and the infraredC=O stretching vibration rdquoAustralian Journal of Chemistry vol16 no 1 pp 7ndash13 1963

[100] K Nakamoto Infra Red Spectra of Inorganic and CoordinationCompounds Wiley-Interscience New York NY USA 1961

[101] I Suzuki ldquoInfrared spectra and normal vibrations of thioa-mides I Thioformamiderdquo Bulletin of the Chemical Society ofJapan vol 35 no 8 pp 1286ndash1293 1962

[102] B Pradhan and D V R Rao Journal of the Indian ChemicalSociety vol 48 p 136 1971

[103] V KMahesh and R S Gupta Indian Journal of Chemistry vol12 no 6 pp 570ndash572 1974

[104] V V Rana S K Sahani M P Swami P C Jain andA K Srivathsava ldquoThiosemicarbazones as ligands-IIIOxovanadyl (IV) complexes of substituted-4-benzamidothi-osemicarbazonesrdquo Journal of Inorganic and Nuclear Chemistryvol 38 no 1 pp 176ndash180 1976

[105] R Pappalardo ldquoLigand field theory and the absorption spectraof MnCl

2and MnBr

2rdquo The Journal of Chemical Physics vol 31

article 1050 1959[106] S Y Shaw and E P Dudek ldquoBidentate bis(N-substituted 2-

acetiminodimedonato)nickel(II) complexesrdquo Inorganic Chem-istry vol 8 no 6 pp 1360ndash1366 1969

[107] D Sutton Electronic Spectra of Transition Metal ComplexesMcGraw-Hill New York NY USA 1968 p 148

[108] D Satyanarayana and V Mohapatra Journal of the IndianChemical Society vol 13 pp 186ndash188 1975

[109] L Sacconi and M Ciampolini ldquo45 Pseudo-tetrahedral struc-ture of some 120572-branched copper(II) chelates with Schiff basesrdquoJournal of the Chemical Society (Resumed) pp 276ndash280 1964

[110] AKMuzundar andPK Bhattacharya ldquoEffect ofmono-ligandson Schiff base complexes-II Copper(II) complexesrdquo Journal ofInorganic and Nuclear Chemistry vol 30 no 4 pp 1116ndash11191968

[111] M Sheela ldquoThe ultra-violet and visible spectra of sometransition metal chelates with N N1015840-bis-(o-hydroxybenzylide-ne)ethylenediamine and NN1015840-bis-(o-hydroxybenzylidene)-o -phenylenediamine and related compoundsrdquo SpectrochimicaActa vol 19 no 1 pp 255ndash270 1963

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Cu(II) Ni(II) and Zn(II) complexes with SB from p-chloro-benzaldehyde with p-chloroaniline [23] Mn(II) Fe(II)Ni(II) and Cu(II) complexes with SB from 5-acetamido-134-thiodiazole-2-sulphonamide and their biologicalactivity [24] Zn(II) Ni(II) and Cu(II) complexes withSB from dicinnamoylmethane and aromatic amines [25]Zn(II) Mn(II) Ni(II) and Cu(II) complexes with SB from2-hydroxy-1-naphthaldehyde and 5-amino-1-naphthol andtheir antibacterial activities [26] Co(II) Ni(II) and Cu(II)complexes with SB from 14-dicarbonylphenyldihydrazidewith 26-diformyl-4-methylphenol [27] Co(II) Ni(II)and Cu(II) complexes with SB from 2-HClBr-6-(4-fluorophenyliminomethyl)phenol [28] Co(II) Ni(II)and Cu(II) complexes with SB from pyrazolealdehydewith 2-aminophenol [29] Co(II) Ni(II) Zn(II) Cd(II)Hg(II) and Cu(II) complexes with SB from benzofuran-2-carbohydrazide and 4-methyl-thio-benzaldehyde andtheir antifungal antibacterial activities being screened[30] Ni(II) and Cu(II) complexes of SB derived from 1-naphthylamine and 2-hydroxy-naphthalene-1-carbaldehyde[31] Fe(III) Ni(II) Cu(II) Co(II) Zn(II) and UO

2(II)

complexes of SB derived from 2-furancarboxaldehyde and o-phenylenediamine [32] VO(II) Co(II) Rh(III) Pd(II) andAu(III) complexes of SB derived from 4-nitrobenzoicacid and thiosemicarbazide and their antibacterialactivity [33] VO(IV) Cu(II) and Ru(II) complexes ofSB derived from 3-hydroxyquinoxaline-2-carboxaldehydeand several amines 18-diaminonaphthalene 23-diaminemaleonitrile 12-diaminocyclohexane 2-iminophenol and4-aminoantipyrine [34] Mn(II) Co(II) Ni(II) Cu(II) andZn(II) complexes of SB derived from 1 10-phenanthrolineand o-vanillidene-2-aminobenzothiazole and o-vanillidene-2-quino-N-(2-pyridyl)-benzenesulfonamide [35] Hg(II)Zn(II) and VO(IV) complexes of SB from S-aminosulfonyl-4-chloro-N-26-dimethylphenyl-2-hydroxybenzamide withsalicylamide [36] Co(II) Cu(II) Ni(II) and Zn(II)complexes of SB derived from several substitutedpyridines with salicylaldehyde [37] Recently new seriesof Co(II) Ni(II) Cu(II) Cd(II) and Hg(II) complexeswere synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime The ligand alongwith its metal complexes has been characterized on thebasis of analytical data IR electronic mass 1HNMR ESRspectral data thermal studies magnetic susceptibility andmolar conductance measurements In order to evaluate theeffect of metal ions upon chelation both the ligand and itsmetal complexes were screened for their antibacterial andantifungal activities by minimum inhibitory concentration(MIC) method [38] Metal chelates [M(HL)

2(H2O)2]X2

(where M = Mn(II) Co(II) Cu(II) Ni(II) or Zn(II) X =NO3

minus or Clndash and HL = SB moiety) have been preparedand characterized by elemental analysis magnetic andspectroscopic measurements (infrared X-ray powderdiffraction and scanning electron microscopy) The SBand its metal chelates have been screened for their in vitroantibacterial activity against four bacteria gram-positive(Staphylococcus aureus) and gram-negative (Escherichiacoli) and two strains of fungus (Aspergillus flavus andCandida albicans) The metal chelates were shown to

possess more antibacterial activity than the free SB chelate[39]

Metal complexes of SBs derived from 2-furancarboxal-dehyde and o-phenylenediamine (L1) and 2-thiophenecar-boxaldehyde and 2-aminothiophenol (HL2) are reported andcharacterized based on elemental analyses IR 1H NMRsolid reflectance magnetic moment molar conductance andthermal analysis (TGA) ConsiderM = Fe(III) Ni(II) Cu(II)Co(II) Zn(II) andUO2(II)The synthesized ligands in com-parison to their metal complexes were also screened for theirantibacterial activity against bacterial species Escherichiacoli Pseudomonas aeruginosa and Staphylococcus Pyogenesas well as fungi (Candida) The activity data show the metalcomplexes to be more potent antibacterials than the parentSB ligand against one or more bacterial species [32]

Synthesis and characterisation of new transition metalcomplexes of SBs derived from 3-hydroxyquinoxaline-2-carboxaldehyde and application of some of these complexesas hydrogenation and oxidation catalysts The subnormalmagnetic moment values substantiate a binuclear structurefor all the Cu(II) complexes favouring square-planar geom-etry and those with magnetic moment of 176 BM favouredoctahedral geometry with mononuclear complex formationwith this SB ligand [34]

It is found that the SBs selected for synthesis for this studyhave not been found in the literature It is also noticed thatmany of the tridentate ligands are found to show strikingbiochemical characters where the azomethine linkage areblended into stable structured inorganic metal chelates In adelicately balanced living system physiological activity is aresult of several chemical and physical processes In such pro-cesses the metal complexes furnished useful drugs and othersubstances as described by selective toxicity in pharmacology[40ndash42] They function by upsetting this delicate balance intwo ways (a) by reinforcing the toxicity of a heavy metalandor (b) by withdrawing the essential metal content fromthe system For example in highly basic iron rich soils themetal ion not available to the rootlets of plants is extractedby spraying Ethylenediaminetetraacetic acidmdash(edta) in theform of a soluble complex Such a mechanism for manyfungicides and bactericides is described as a partition effector cooperative effect [43] Thus to evaluate the chemicalsubstances as fungicides and bactericides the followingmethods are used commonly (1) slide germination method[44ndash46] (2) test-tube dilution method [47] (3) cell-volumeassaymethod [48] (4) inhibition-zone ormodified paper discmethod [49ndash51] and (5) poisoned food technique [50]

Three important rice pathogens were selected for thepresent study two fungal species and a bacterium Thereasons for selecting these species are given in brief (1)Rhizoctonia solani causes sheath blight [52 53] which is aserious disease of the rice-cropThe symptoms are (a) grayishwhite patches and (b) yellowing of leaves This spreads veryquickly and causes enormous loss It also causes severalother diseases on many economically important commercialcrops (2) Acrocylindrium oryzae causes sheath rot of paddydecaying the sheath and was first reported [54ndash56] in IndiaA large number of fungicides are evaluated against thisorganism in vitro and in vivo A few of them are in use to




















C

OH

OH

HN

O

+

+

OC

H

O

C

OH

OH

OH

OHOH

OHOH

OH

OH

OH

OH

NH

O

N C

H

O

CHN

O

CO

C NH

NH

NH

O

N C

OH

CHN

O

+

OC

H

O

C

O

N C

H

O

CHN

S

+ CON CC

S

C HN

O

+

OHO

HO

O

CO

C

OH

HN N

OO

O

C



Thiosemicarbazide






L2

L1

L3

L4

L5

BHFH

BHFH

HAEP

BFH

BHDH

O

O


L6

NH2

NH2

NH2

NH2

NH2

minusH2O

minusH2O

minusH2O

minusH2O

minusH2O

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3


H2N

H3C

H2N

N998400

N998400

N998400

N998400

Scheme 1






210 White 6300(6318)

450(438)



308 Grey 5002(5010)

290(278)

1000(973)

2095(2209) mdash 57535 Loss of 8H


280 Green 4720(4744)

345(329)

950(922)

2000(2094) mdash 30355 Loss of 8H


265 Red 5000(5025)

350(349)

920(976)

2000(2047) mdash 28683 Loss of H2O


280 Green 5600(5617)

400(390)

1100(1092)

1150(1145) mdash 51270 Loss of 6H


260 Pink 4255(4270)

330(326)

851(829)

1750(1746)

1050(1052) 67512 Loss of 8H


320 Red 4050(4058)

280(282)

792(789)

1600(1574)

2000(2001) 70970 Loss of 4H


280 Yellow 4450(4465)

298(310)

812(868)

1700(1690)

1000(1101) 64500 Loss of 15H2O


285 Grey 4400(4414)

300(306)

850(857)

1500(1560)

1074(1087) 65314 Loss of 8H





215 Yellow 6300(6318)

500(491)



305 Green 4705(4736)

350(342)

750(737)

1600(1672)

950(935) 38010 Loss of 4H


270 Red 5700(5726)

420(414)

877(891)

950(934) mdash 62870 Loss of 2H


260 Brown 5750(5761)

435(448)

901(896)

1000(943) mdash 63093 mdash


305 Black 4555(4564)

435(380)

723(710)

1452(1416)

950(900) 78870 Loss of 2H


285 Brown 5800(5802)

393(387)

900(902)

1000(878) mdash 62050 Loss of 4H


300 Grey 4420(4428)

329(334)

725(738)

1286(1343)

920(946) 75888 Loss of 2C and 2H





193 Brown 5200(5218)

540(531)



310 Brown 4000(4021)

350(335)

1550(1564)



305 Brown 3900(3931)

350(328)

1530(1529)

2100(2136) mdash 54952 Loss of NH2


295 Brown 3570(3589)

430(432)

930(930)



300 Green 3050(3088)

351(354)

891(901)

1800(1797)

1100(1142) 62170 Loss of 2N 2C add 05H2O


265 Green 3500(3523)

421(359)

900(913)

1550(1696)

1025(1158) 61312 Loss of NH2


310 Grey 3450(3462)

320(417)

899(897)

1574(1633) 31200 Loss of NH2






182 Yellow 6750(6763)

500(469)




(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O


pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O


300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O





240 Yellow 6000(6002)

500(466)



300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H


305 Green 4055(4063)

390(391)

730(729)












1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




















C

OH

OH

HN

O

+

+

OC

H

O

C

OH

OH

OH

OHOH

OHOH

OH

OH

OH

OH

NH

O

N C

H

O

CHN

O

CO

C NH

NH

NH

O

N C

OH

CHN

O

+

OC

H

O

C

O

N C

H

O

CHN

S

+ CON CC

S

C HN

O

+

OHO

HO

O

CO

C

OH

HN N

OO

O

C



Thiosemicarbazide






L2

L1

L3

L4

L5

BHFH

BHFH

HAEP

BFH

BHDH

O

O


L6

NH2

NH2

NH2

NH2

NH2

minusH2O

minusH2O

minusH2O

minusH2O

minusH2O

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3


H2N

H3C

H2N

N998400

N998400

N998400

N998400

Scheme 1






210 White 6300(6318)

450(438)



308 Grey 5002(5010)

290(278)

1000(973)

2095(2209) mdash 57535 Loss of 8H


280 Green 4720(4744)

345(329)

950(922)

2000(2094) mdash 30355 Loss of 8H


265 Red 5000(5025)

350(349)

920(976)

2000(2047) mdash 28683 Loss of H2O


280 Green 5600(5617)

400(390)

1100(1092)

1150(1145) mdash 51270 Loss of 6H


260 Pink 4255(4270)

330(326)

851(829)

1750(1746)

1050(1052) 67512 Loss of 8H


320 Red 4050(4058)

280(282)

792(789)

1600(1574)

2000(2001) 70970 Loss of 4H


280 Yellow 4450(4465)

298(310)

812(868)

1700(1690)

1000(1101) 64500 Loss of 15H2O


285 Grey 4400(4414)

300(306)

850(857)

1500(1560)

1074(1087) 65314 Loss of 8H





215 Yellow 6300(6318)

500(491)



305 Green 4705(4736)

350(342)

750(737)

1600(1672)

950(935) 38010 Loss of 4H


270 Red 5700(5726)

420(414)

877(891)

950(934) mdash 62870 Loss of 2H


260 Brown 5750(5761)

435(448)

901(896)

1000(943) mdash 63093 mdash


305 Black 4555(4564)

435(380)

723(710)

1452(1416)

950(900) 78870 Loss of 2H


285 Brown 5800(5802)

393(387)

900(902)

1000(878) mdash 62050 Loss of 4H


300 Grey 4420(4428)

329(334)

725(738)

1286(1343)

920(946) 75888 Loss of 2C and 2H





193 Brown 5200(5218)

540(531)



310 Brown 4000(4021)

350(335)

1550(1564)



305 Brown 3900(3931)

350(328)

1530(1529)

2100(2136) mdash 54952 Loss of NH2


295 Brown 3570(3589)

430(432)

930(930)



300 Green 3050(3088)

351(354)

891(901)

1800(1797)

1100(1142) 62170 Loss of 2N 2C add 05H2O


265 Green 3500(3523)

421(359)

900(913)

1550(1696)

1025(1158) 61312 Loss of NH2


310 Grey 3450(3462)

320(417)

899(897)

1574(1633) 31200 Loss of NH2






182 Yellow 6750(6763)

500(469)




(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O


pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O


300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O





240 Yellow 6000(6002)

500(466)



300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H


305 Green 4055(4063)

390(391)

730(729)












1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


C

OH

OH

HN

O

+

+

OC

H

O

C

OH

OH

OH

OHOH

OHOH

OH

OH

OH

OH

NH

O

N C

H

O

CHN

O

CO

C NH

NH

NH

O

N C

OH

CHN

O

+

OC

H

O

C

O

N C

H

O

CHN

S

+ CON CC

S

C HN

O

+

OHO

HO

O

CO

C

OH

HN N

OO

O

C



Thiosemicarbazide






L2

L1

L3

L4

L5

BHFH

BHFH

HAEP

BFH

BHDH

O

O


L6

NH2

NH2

NH2

NH2

NH2

minusH2O

minusH2O

minusH2O

minusH2O

minusH2O

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3


H2N

H3C

H2N

N998400

N998400

N998400

N998400

Scheme 1






210 White 6300(6318)

450(438)



308 Grey 5002(5010)

290(278)

1000(973)

2095(2209) mdash 57535 Loss of 8H


280 Green 4720(4744)

345(329)

950(922)

2000(2094) mdash 30355 Loss of 8H


265 Red 5000(5025)

350(349)

920(976)

2000(2047) mdash 28683 Loss of H2O


280 Green 5600(5617)

400(390)

1100(1092)

1150(1145) mdash 51270 Loss of 6H


260 Pink 4255(4270)

330(326)

851(829)

1750(1746)

1050(1052) 67512 Loss of 8H


320 Red 4050(4058)

280(282)

792(789)

1600(1574)

2000(2001) 70970 Loss of 4H


280 Yellow 4450(4465)

298(310)

812(868)

1700(1690)

1000(1101) 64500 Loss of 15H2O


285 Grey 4400(4414)

300(306)

850(857)

1500(1560)

1074(1087) 65314 Loss of 8H





215 Yellow 6300(6318)

500(491)



305 Green 4705(4736)

350(342)

750(737)

1600(1672)

950(935) 38010 Loss of 4H


270 Red 5700(5726)

420(414)

877(891)

950(934) mdash 62870 Loss of 2H


260 Brown 5750(5761)

435(448)

901(896)

1000(943) mdash 63093 mdash


305 Black 4555(4564)

435(380)

723(710)

1452(1416)

950(900) 78870 Loss of 2H


285 Brown 5800(5802)

393(387)

900(902)

1000(878) mdash 62050 Loss of 4H


300 Grey 4420(4428)

329(334)

725(738)

1286(1343)

920(946) 75888 Loss of 2C and 2H





193 Brown 5200(5218)

540(531)



310 Brown 4000(4021)

350(335)

1550(1564)



305 Brown 3900(3931)

350(328)

1530(1529)

2100(2136) mdash 54952 Loss of NH2


295 Brown 3570(3589)

430(432)

930(930)



300 Green 3050(3088)

351(354)

891(901)

1800(1797)

1100(1142) 62170 Loss of 2N 2C add 05H2O


265 Green 3500(3523)

421(359)

900(913)

1550(1696)

1025(1158) 61312 Loss of NH2


310 Grey 3450(3462)

320(417)

899(897)

1574(1633) 31200 Loss of NH2






182 Yellow 6750(6763)

500(469)




(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O


pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O


300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O





240 Yellow 6000(6002)

500(466)



300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H


305 Green 4055(4063)

390(391)

730(729)












1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






210 White 6300(6318)

450(438)



308 Grey 5002(5010)

290(278)

1000(973)

2095(2209) mdash 57535 Loss of 8H


280 Green 4720(4744)

345(329)

950(922)

2000(2094) mdash 30355 Loss of 8H


265 Red 5000(5025)

350(349)

920(976)

2000(2047) mdash 28683 Loss of H2O


280 Green 5600(5617)

400(390)

1100(1092)

1150(1145) mdash 51270 Loss of 6H


260 Pink 4255(4270)

330(326)

851(829)

1750(1746)

1050(1052) 67512 Loss of 8H


320 Red 4050(4058)

280(282)

792(789)

1600(1574)

2000(2001) 70970 Loss of 4H


280 Yellow 4450(4465)

298(310)

812(868)

1700(1690)

1000(1101) 64500 Loss of 15H2O


285 Grey 4400(4414)

300(306)

850(857)

1500(1560)

1074(1087) 65314 Loss of 8H





215 Yellow 6300(6318)

500(491)



305 Green 4705(4736)

350(342)

750(737)

1600(1672)

950(935) 38010 Loss of 4H


270 Red 5700(5726)

420(414)

877(891)

950(934) mdash 62870 Loss of 2H


260 Brown 5750(5761)

435(448)

901(896)

1000(943) mdash 63093 mdash


305 Black 4555(4564)

435(380)

723(710)

1452(1416)

950(900) 78870 Loss of 2H


285 Brown 5800(5802)

393(387)

900(902)

1000(878) mdash 62050 Loss of 4H


300 Grey 4420(4428)

329(334)

725(738)

1286(1343)

920(946) 75888 Loss of 2C and 2H





193 Brown 5200(5218)

540(531)



310 Brown 4000(4021)

350(335)

1550(1564)



305 Brown 3900(3931)

350(328)

1530(1529)

2100(2136) mdash 54952 Loss of NH2


295 Brown 3570(3589)

430(432)

930(930)



300 Green 3050(3088)

351(354)

891(901)

1800(1797)

1100(1142) 62170 Loss of 2N 2C add 05H2O


265 Green 3500(3523)

421(359)

900(913)

1550(1696)

1025(1158) 61312 Loss of NH2


310 Grey 3450(3462)

320(417)

899(897)

1574(1633) 31200 Loss of NH2






182 Yellow 6750(6763)

500(469)




(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O


pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O


300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O





240 Yellow 6000(6002)

500(466)



300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H


305 Green 4055(4063)

390(391)

730(729)












1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






182 Yellow 6750(6763)

500(469)




(4242)325(295)

810(825)

1350(1532)

1952(2091) 67900 Loss of 15H2O


pH 85310 Red 5500

(5538)350(385)

1050(1077)

1000(1000)

1252(1365) 52000 Loss of 25H2O


300 Red 5850(5842)

400(406)

1090(1136)

1000(1033) mdash 49294 Loss of H2O





240 Yellow 6000(6002)

500(466)



300 Green 4700(4706)

300(314)

752(732)

1000(1359)

925(928) 76500 Loss of 2H


305 Green 4055(4063)

390(391)

730(729)












1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





1 DHA-L6C8H8O4

109 Colorless 5700(5717)

500(476) mdash 16808 mdash


285 Green 5500(5541)

425(461)

1000(1000) 52026 Loss of two H2O


305 Green 4550(4561) mdash 1175

(1210) 42094 mdash

07

08

09

10

11

12

13

14

15

16

17

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)(d)




2(H2O)]




300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)

(c)

(d)




2(H2O)]





Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table7Ch

aracteris

ticIR

dataforthe

L1-BHFH

(tridentatendashO

ndashOand

ndashN)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

evO

ndashHandvN

ndashHe

vC=O

evC

=Ne

vC=O

phenolic

eMndashO

MndashN

orM

ndashCle

1BH

FH-L1c

de

mdash3260

a1640

(s)

1610

(s)

1220

(s)b

mdash2

[Cu(BH

FH)]

2mdash

Absent

Absent

1590

(d)

1250

(s)

490475430

3[Cu(BH

FH)H

2O]

3420ndash3220(b)

Absent

Absent

1590

(s)

1190

830(s)485430410

4[N

i(BHFH

)H2O

]3500ndash340

0(b)

Absent

Absent

1620

(s)1590

(s)

1255

(s)

830(s)580560

5[N

i(BHFH

) 2]

mdash3210

(s)

Absent

1610

(d)

1250

(s)

450370

6[C

o(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3210

(s)

Absent

1615

(s)1580(s)

1255

(s)

870(s)55044

0360

7[Fe(BH

FH)C

l 2]2

mdash3220

(s)

Absent

1615

(s)1585

(s)

1250

(s)

55044

0360

8[M

n(BH

FH)(H

2O)C

l] 23500ndash340

0(b)

3220

(s)

Absent

1610

(s)1575

(s)

1245

(s)

845ndash835(d)44

0390350

9[V

O(BHFH

)Cl] 2

mdash3175

(s)

Absent

1610

(s)1585

(s)

1250

(s)

970(V

=O)f

550420370

a Overla

pof

hydrogen

bond

edOndashH

andNndashH

bStretching

frequ

encycNochange

invN

=Nat1075

cmminus1Shyam

alandKa

le[88]dNochange

insymmetric

andasym

metric

frequ

encies

offurfuralrin

gvC

ndashOndashC

at1020


oninvolvem

ento

fOof

furfuralrin

gin

complexation

e Theenolizationof

thehydrazideresid

ueandthesubsequent

deproton

ationof

both

thehydroxylgrou

psor

cleavageof

hydrogen

bond

form

ingMndashO

bond

scon

firmed

byvC

ndashOph

enolicshiftdou

bletfortwovC

=Ngrou

ps(one

azom

ethine

participatingin

complex

form

ationandon

eformed

duetoenolizationof

ligand)absence

ofvC

=Oand

newband

sfor

vNndashH

vC=

NM

ndashOand

MndashN

vibrationsN

akam

oto[91]U

enoandMartell[9293]

f Selb

in[94]





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





300

400

500

600

700

800

900

1100

1000

1200

1300

1400

1500

1600

(a)

(b)


3] (b) BFH-[Cr(BFH)

2(C1)(H

2O)] (c)


2

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2O)]2 (b) BHEH-[Mn

(BHEH)2]

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)



2O)]2 (c)


300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)

(d)



(H2O)2]2


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table9Ch

aracteris

ticIR

dataforthe

L3-H

AEP

(tridentatendashO

ndashNand

ndashS)a

ndits

participationin

complex

form

ationwith

metalions

Snu

mber

Com

plex


ubletw=weakvw

=very

weak)

Coo

rdwater

vOndashH

avN

ndashH2

bvC

=Nd

vC=O

phenolic

cvC

=Slowastlowast

MndashO

MndashN

and

MndashSlowastlowast

1HAEP

-L3

mdash3400

(b)

3320

(s)3280

(s)

1630

(s)

1270

(s)

1280

(s)

mdash2

[Cu(HAEP

)]2

mdash3440

(s)c

3320

(s)3280

(s)

1640

1610(s)

1295

(s)

1225

(s)

85050040

03

[Ni(H

AEP

) 2]

mdash3460

(s)

3320ndash3280(s)

1640

1610(s)

1295

(s)

1220

(w)

85060

0ndash40

04

[Co(HAEP

)(H

2O) 2] 2

3560

(b)

3480

(b)

3320

(b)3280

(b)

1610ndash1620(b)

1280

(s)

1220

(w)

85057047041040

05

[Fe(HAEP

)(H

2O)C

l] 23560

(b)

3480

(b)

3320

(s)3280

(s)

1640

1620(d)

1295

(s)

1220

(w)

85057548040

06

[Cr(HAEP

)(H

2O)C

l] 23500ndash3450(b)

3480

(b)

3320

(s)3280

(s)

16051595(d)

1280

(s)

1010

(w)

85052044

0295

7[V

O(H

AEP

)(H

2O) 2]

3560

(b)

3460

(s)

3320

(s)3280

(s)

1600ndash1610

1290

(s)

mdash970(V

=O)850310300

lowastlowastLigand

existsinldquoth

ionerdquoform

andno


inthesolid

stateas

theexpected

vSndashH

band

at2570


isno

tobservedandvC


o[65]SahaandDeepak

[66]


i[101]Pradh

anandRa

o[102]

a Overla

poftwohydroxylgrou

psofresacetoph

enon

emoietya

ndhydrogen

bond

ingtosomee

xtentb Sym

metric

andasym

metric

frequ

encies

ofNH

2grou

pno

tpartic

ipated

incomplexation

c New

sharpband

offre

endashOHindicatesd

eprotonatio

nandcoordinatio

nd N

ewvC

=Ngrou

pdu


inoriginalvC

=Ngrou

pof

azom

ethine










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)(b)

(c)


2 (b) BHFH (AT ph


2] (d) HAEP

[Ni(HAEP)]2



300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

(a)

(b)(c)


2 (b) BHFH (AT ph


[Cu(HAEP)]2






















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




















1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1



280061827013330


O

OCl

ClN

ON

O

O

O

V2minus

V2minus 154MndashM

2



250001492013000 O

OCl

ClN

ON

O

O

OV2minus

V2minus 163MndashM

3



250002220013560

NO

O

S

OH2

OH2

V2minus 172

4


coordination

25000-2220016100

O

N

N

O

O

OH2

V2minus 174

5



equatorial plane

258001538013150

N

O

O

O

OOH2

V3minus171

6


plane

300002550018180

O

OO

O OOH2

V2minus 172








1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1



plane

2793017390


Cl

Cl N

N

O

OS

SOH2

OH2


2



2787817420

Cl

Cl

O

NO

N

O

O

OH2

OH2

CrCr 355MndashM

3



equatorial plane

2667017500 Cl

N

N

O

O

Cr3minusH2O 388

4


equatorial plane

2898017390 CrCr

Cl

Cl

O

O

O

O

O

ON+

N+

374MndashM

5[Cr(DHA)3]


2667018200 O

O

O

O

O

O

Crminus389








1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1



plane

27030212701961018180 6A1g-4Eg 4A1g (G)



MnMn

Cl

ClN

N

O

OO

O

H2O

OH2

544MndashM

2[Mn(BHEH)2]


2667017240 O

NH

O

O

O

NH

Mnminus 592




1



23260217401904017540

Cl

ClN

N

O

Cl

Cl

OO

OFeminus Feminus

570MndashM

2


2667022220185201739015600

FeFe

Cl

ClN

N

O

OO

O

H2O

OH2

573MndashM

3


Extremelyweak

transitions

NCl

S

N

ClSO

OFeminusFeminus

H2O

OH2

588MndashM









1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1




31250200001852015400


CoCo

Cl

ClN

N

O

OO

O

OH2

H2O

458MndashM

2


equatorial plane

1975018450157008430

Co

O

N

N

O

OO 392

3




2703017700156308330

S

S

Cl

Cl

O

O

N

NH

OH2

H2O












1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1



plane

2613018100



O

N

O

H2O

Ni+Dia

2[Ni(BHFH)2]


2630015000

9520 (w)



O N

N

O

O

Niminus 324

3[Ni(BHEH)2]


26670 (s)2000013100

8200 (w)


3A2g-3T1g (P)3A2g-2T1g 3T1g (F)


O

O N

N

O

O

Niminus 291

4



plane

2703016600




Ni

N

O

S

NiN

O

S

DiaMndashM








1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1



28570 (sm)14300 (b)


O

NO

O

ON

Cuminus

Cuminus

150MndashM

2



27030 (s)18180 (b)

Cu

N

O

O

OH2

204

3


ndashN coordination

2665017540

N

ClO

O

Cuminus

191

4




256401538013330

S

S

ON


MndashM





4 Conclusions
















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















Acknowledgment


References













































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







































































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





































































2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


























2and MnBr


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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Research Article Characterization of Complexes Synthesized ...downloads.hindawi.com/archive/2014/736538.pdf · Research Article Characterization of Complexes Synthesized Using Schiff