Synthesis and Reactivity of Heterotopic Ligands Containing ... ... or sulfur donors. Ligands incorporating

  • View
    1

  • Download
    0

Embed Size (px)

Text of Synthesis and Reactivity of Heterotopic Ligands Containing ... ... or sulfur donors. Ligands...

  • UNIVERSITATEA BABEŞ–BOLYAI Facultatea de Chimie şi Inginerie Chimică UNIVERSITÄT LEIPZIG Fakultät für Chemie und Mineralogie

    Summary of the Ph. D. Thesis

    Synthesis and Reactivity of Heterotopic Ligands Containing As/P, As/S/P and As/S/As

    as Donor Atoms Scientific advisors Ph.D. student Prof. Dr. Luminiţa Silaghi-Dumitrescu Imola Bartók (căs. Sárosi) Prof. Dr. Evamarie Hey-Hawkins

    Cluj-Napoca –2012–

  • JURY

    PRESIDENT

    Conf. Dr. Cornelia MAJDIK

    REVIEWERS

    CSI Dr. Otilia COSTIŞOR - Institutul de Chimie Timişoara al Academiei

    Române, Timişoara.

    Prof. Dr. Simona Luminiţa OPREAN - Universitatea de Medicină şi Farmacie

    Iuliu Haţieganu, Cluj-Napoca.

    Acad. Prof. Dr. Ionel HAIDUC - Facultatea de Chimie şi Inginerie Chimică,

    Universitatea Babeş-Bolyai, Cluj-Napoca, President of the Romanian Academy.

    Date of public defense: February 27, 2012

  • CONTENTS (as in the full text)

    Introduction .......................................................................................................................5

    1. Literature overview....................................................................................................... 5

    1.1. Hemilabile ligands ................................................................................................ 5

    1.2. Heterotopic ligands containing P,S and As,S as donor atoms .............................. 7

    1.2.1 Synthesis and coordination chemistry of the EPh2(SPh) ligands................... 7

    1.2.2 Synthesis and coordination chemistry of the ligands 1-EPh2-2-SH-C6H4 ... 12

    1.2.3 Synthesis and coordination chemistry of the ligands 2,6-(Ph2PCH2)2C6H3SH

    and 2,6-(Ph2P)2C6H3SH ........................................................................................ 17

    Original contributions..................................................................................................... 23

    2. Aims of this work ....................................................................................................... 23

    3. Heterotopic ligands containing As/P, As/S/P and As/S/As as donor atoms............... 26

    3.1. Heterotopic ligands containing As/P as donor atoms ......................................... 26

    3.1.1 Synthesis of 1-PPh2-2-S(AsPh2)C6H4 (1) and 1-AsPh2-2-S(PPh2)C6H4 (2) 26

    3.1.2 Molecular structure of 1-PPh2-2-S(AsPh2)C6H4 (1) .................................... 27

    3.1.3 Theoretical calculations for 1-PPh2-2-S(AsPh2)C6H4 (1) ............................ 28

    3.2. Heterotopic ligands containing As/S/P and As/S/As as donor atoms................. 30

    3.2.1 Synthesis of 1-PPh2-2-S(C4H9)-3-AsPh2-C6H3 (3, SPAs), 1,3-AsPh2-2-

    S(C4H9)C6H3 (4, SAs2) and 1-PPh2-2-SH-3-AsPh2-C6H3 (5, SHPAs) ................ 31

    3.2.2 Molecular structures of 4a, SPAs, SAs2 and SHPAs.................................. 33

    3.2.3 Theoretical calculations for SPAs (3) and SHPAs (5) ................................ 37

    4. Coordination chemistry of 1-PPh2-2-S(AsPh2)C6H4 (1) with transition metal

    complexes ....................................................................................................................... 40

    4.1. Coordination chemistry of 1 with group 10 metal(II) complexes ...................... 40

    4.1.1 Synthesis and spectroscopic properties of Ni (6), Pd (7, 8) and Pt (9, 10)

    complexes.............................................................................................................. 40

    4.1.2 Molecular structures of Pd (7, 8) and Pt (9, 10) complexes......................... 45

    4.1.3 Theoretical calculations for Pd (7, 8) and Pt (9, 10) complexes .................. 48

    4.2. Coordination chemistry of 1 with metal carbonyl complexes (M = Mo, Mn, Fe)

    ................................................................................................................................... 50

  • 4.2.1 Synthesis and molecular structure of [MoCp(CO)2{(SC6H4-2-PPh2)-κS,P}]

    (11) ........................................................................................................................ 50

    4.2.2 Synthesis and molecular structure of [Mn2(CO)7(µ-AsPh2){(SC6H4-2-PPh2)-

    κS,P}] (12) and [Mn2(CO)8(µ-AsPh2)2] (13) ........................................................ 52

    4.2.3 Synthesis and molecular structure of [Fe(CO)2{(SC6H4-2-PPh2)-κ 2 S,P)}2]

    (14) ........................................................................................................................ 56

    4.2.4 Synthesis and molecular structure of [FeCp(CO){(SC6H4-2-PPh2)-κS,P}]

    (15) ........................................................................................................................ 59

    5. Coordination chemistry of SPAs (3) with rhodium and group 10 metal(II) complexes

    ........................................................................................................................................ 61

    5.1. Synthesis and molecular structure of [RhCl2{(Rh(cod)(SC6H3-2-PPh2-3-AsPh2)-

    κS,P)-κS,As}2][RhCl2(cod)] (16) ............................................................................... 61

    5.2. Synthesis and molecular structure of trans-[Ni{(SC6H3-2-PPh2-3-AsPh2)-

    κ2S,P}2] (17) .............................................................................................................. 64

    5.3. Synthesis and molecular structure of [{Pd2Cl2(SC6H3-2-PPh2-3-AsPh2)}2(µ-Cl)2]

    (18)............................................................................................................................. 67

    5.4. Synthesis and molecular structure of cis-[Pt{(SC6H3-2-PPh2-3-AsPh2)-κ 2 S,P}2]

    (19a)........................................................................................................................... 70

    5.5. Synthesis and molecular structure of [Pt{(PtI2(SC6H3-2-PPh2-3-AsPh2)-κS,P)-

    κS,As}2] (20) .............................................................................................................. 73

    5.6. Theoretical study of the cis-trans isomerism of 17 and 19a............................... 76

    6. Coordination chemistry of trans-[Ni{(SC6H3-2-PPh2-3-AsPh2)-κ 2 S,P}2] (17) with

    group 10 metal(II) complexes ........................................................................................ 79

    6.1. Molecular structure of [{Pd2Cl2(OH2)(SC6H3-2-PPh2-3-AsPh2)}2] (21)............ 81

    6.2. Molecular structure of [{NiI(µ-S-SC6H4-2-PPh2)-κ 2 S,P}2] (22) ........................ 84

    7. General conclusions.................................................................................................... 87

    8. Experimental section .................................................................................................. 91

    8.1. Materials and methods ........................................................................................ 91

    8.2. Analytical methods ............................................................................................. 91

    8.3. Theoretical methods............................................................................................ 92

    8.4. Synthesis of starting materials ............................................................................ 93

    8.4.1 Diphenylchloroarsine ................................................................................... 93

  • 8.4.2 1-EPh2-2-SH-C6H4 (E = P, As) .................................................................... 95

    8.4.3 1-EPh2-2-S(C4H9)C6H4 (E = P, As (4a))...................................................... 96

    8.5. Synthesis of heterotopic ligands containing As/P, As/S/P and As/S/As as donor

    atoms.......................................................................................................................... 98

    8.5.1 1-PPh2-2-S(AsPh2)C6H4 (1) ......................................................................... 98

    8.5.2 1-AsPh2-2-S(PPh2)C6H4 (2) ......................................................................... 99

    8.5.3 1-PPh2-2-S(C4H9)-3-AsPh2-C6H3 (3, SPAs).............................................. 100

    8.5.4 1,3-AsPh2-2-S(C4H9)C6H3 (4, SAs2) ......................................................... 101

    8.5.5 1-PPh2-2-SH-3-AsPh2-C6H3 (5, SHPAs)................................................... 102

    8.6. Synthesis of metal complexes with 1-PPh2-2-S(AsPh2)C6H4 (1) ..................... 103

    8.6.1 trans-[Ni{(SC6H4-2-PPh2)-κ 2 S,P}2] (6) ..................................................... 103

    8.6.2 [PdCl{(µ-S-SC6H4-2-PPh2)-κ 2 S,P}]3 (7).................................................... 104

    8.6.3 [(cis-Pd{(µ-S-SC6H4-2-PPh2)-κ 2 S,P}2)-PdCl2-PdCl{(µ-S-SC6H4-2-PPh2)-

    κ2S,P}] (8) ........................................................................................................... 104

    8.6.4 [PtI{(µ-S-SC6H4-2-PPh2)-κ 2 S,P}]3 (9)....................................................... 105

    8.6.5 [(cis-Pt{(µ-S-SC6H4-2-PPh2)-κ 2 S,P}2)-PtI2-PtI{(µ-S-SC6H4-2-PPh2)-κ

    2 S,P}]

    (10) ...................................................................................................................... 105

    8.6.6 [MoCp(CO)2{

Related documents