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transfer hydrogenationL = NR2hydrogenation of ketonesL = PR2hydrogenolysis of epoxides and imides
RuNPh
Ph N
Ts
ClHH
Rn
RuL
N ClHH
N
RuX
H
MOLECULAR CATALYSTS WITH M/NH BIFUNCTIONAL UNITS
Nu H
: arene, Cp* ligand
N
RuX
H
Nu
H
X : N, PNu H : H2, (CH3)2CHOH, HCOOH, CH2(COOR)2
amine complexamide complex
RuCl
Cl
Rn
NH2
THIS WORK
A B A BNu H
catalyst precursor :
REPORTED EXAMPLES OF η1: η6-(AMINOARENE)Ru COMPLEXES
Kurosawa, Inorg. Chim. Acta, 2000
RuPh3P
Cl NH2
BF4
η6 −arene → η1 : η6 −L−arene
n−2
NH2 1) Birch reductionNH3Cl
EtOHreflux
2) HCl
n = 2, 3
(CH2)nNH3Cl
RuCl
Cl 2
RuCl
H2NN
SO2
PhPh
Wills, J. Am. Chem. Soc., 2004
RuCl
Cl 2
SO2
HN
Ph
NH3Cl
Ph
2-propanolreflux
N(C2H5)3
RuCl3 xH2O
n-1 n-1
η1−L → η1 : η6 −L−arene
THIS WORK : INTRAMOLECULAR ARENE DISPLACEMENT REACTION
NH2
CO2Et
RuCl
Cl 2
+
η1 −NH2 complex η1:η6−tethered complex
∆ RuCl
ClNH2
RuCl
ClNH2
EtOCO
EFFECT OF SUBSTITUENTS FOR η1: η6-(AMINOARENE)Ru COMPLEXES
chlorobenzene140 °C
RuCl
ClNH2
yield, %a
H >99m-CH3
p-CH3
R
>9962
80o-Si(CH3)3
m-Si(CH3)3
p-Si(CH3)3
88
90
[Ru] = 0.02 M. aIsolated yield.
time, h
21
20
22
2
18
m,p-(CH3)2 6717
RuCl
ClNH2
EtOCOR R
EFFECT OF STRUCTURE OF AMINOARENES
H 94m-Si(CH3)3
p-Si(CH3)3 56
1622
NH2R
OY
R
yield, %aR
p-Si(CH3)3
p-Si(CH3)3
time, h
21
Y
CO
69
<1<1
CH2
NH2
NH2
R1 R2
yield, %aR time, hyield, %aR1 time, hR2
CH3
CO2CH3
1813H
9898
CH3
[Ru] = 0.02 M. aIsolated yield.
SYNTHESIS OF CATIONIC ARENE−Ru COMPLEXES
BF4
RuPh3P
Cl
(CH2)2NH3Cl
methanolreflux, 20 h56% yield
RuCl
ClNH2 Cl
methanolrt, 15 h42% yield
this work
RuPh3P
ClNH2
+ +PPh3 + AgBF4 NaOH + NaBF4
Kurosawa, Inorg. Chim. Acta, 2000
Ru−C(1) 2.152(9) Ru−C(2) 2.221(9) Ru−C(3) 2.276(8) Ru−C(4) 2.241(7) Ru−C(5) 2.197(6) Ru−C(6) 2.174(7) Ru−Cl 2.404(2) Ru−N 2.157(7) Ru−P 2.360(2)P−Ru−Cl 87.90(7)P−Ru−N 92.0(2)N−Ru−Cl 84.8(2)
Selected bond lengths[Å] and angles[°]
STEREOSELECTIVE FORMATION OF PHOSPHINE COMPLEXES
methanolreflux, 18 h
PPh3AgSbF6
RuCl
ClNH2
(CH3)3Si
RuCl
PPh3
NH2
SbF6(CH3)3Si
anti 70% yield
phosphine complex with ethylene tether
single diastereomer (31P NMR)
+
R1 (I > 2σ) = 0.094wR2 = 0.175P-1 (#2)Z = 2
Ru−C(1) 2.211(4) Ru−C(2) 2.255(4) Ru−C(3) 2.267(5) Ru−C(4) 2.217(5) Ru−C(5) 2.186(6) Ru−C(6) 2.222(6) Ru−Cl 2.3969(13) Ru−N 2.135(4) Ru−P 2.3541(12)
Selected bond lengths[Å] and angles[°]
P−Ru−Cl 86.13(4)P−Ru−N 90.93(13)N−Ru−Cl 81.05(13)
CH2Cl2rt, 24 h
RuCl
PPh3
NH2
(CH3)3Si SbF6
RuCl
ClNH2
(CH3)3Si
anti 52% yieldsingle diastereomer (31P NMR)
phosphine complex with propylene tether
PPh3AgSbF6
+
R1 (I > 2σ) = 0.053wR2 = 0.143P-1 (#2)Z = 4
SYNTHESIS OF CATIONIC ISOCYANIDE COMPLEX
RuCl
Cl
NH2
(CH3)3Si
RuCl
CNt-C4H9
NH2
(CH3)3Si
+ +
SbF6
CH2Cl2, rt2 h, 88% yield
IR νN≡C 2201 cm-1
AgSbF6 t-C4H9NC
RuCl
CNt-C4H9
NH2
(CH3)3SiSbF6
IR νN≡C 2197 cm-1
+ +CH2Cl2, rt2 h, 49% yield
AgSbF6 t-C4H9NCRuClCl
NH2
(CH3)3Si
Ru−Cl 2.3911(13) Ru−N(1) 2.142(3) Ru−C(13) 1.989(4) N(2)−C(13) 1.142(5)
C(13)−Ru−Cl 83.34(13)C(13)−Ru−N 86.91(12)N−Ru−Cl 81.62(11)
Selected bond lengths[Å]and angles[°]
t-C4H9NCAgSbF6
CH2Cl2rt, 1 h
Rut-C4H9NC
ClNH2
(CH3)3Si SbF6
RuCl
ClNH2
(CH3)3Si
RuCl
CNt-C4H9
NH2
(CH3)3Si SbF6
syn 16% yield anti
isocyanide complex with propylene tether
+
IR νN≡C 2193 cm-1
R1 (I > 2σ) = 0.044wR2 = 0.090P-1 (#2)Z = 2
Si(CH3)3
RuCl
Cl 2 R1 = n-C6H13
7 9aDetermined by 1H NMR.
yield, %a
EFFECT OF AMINO-TETHER IN HYDROGEN TRANSFER
O Ru catt-C4H9OK
OH
H2-propanol30 °C, 1 h
ketone:Ru:t-C4H9OK = 10:1:1, [ketone] = 0.1 M
RuCl
ClNH2
(CH3)3Si
RuCl
ClNH2
(CH3)3Si
28 >99yield, %a
RuCl
ClNH2
(CH3)3Si
<1 (without base)
RuCl
ClNR1H2
(CH3)3Si
aDetermined by 1H NMR.
HYDROGEN TRANSFER USING CATIONIC COMPLEXES
O Ru catt-C4H9OK
OH
H2-propanol30 °C, 1 h
ketone:Ru:t-C4H9OK = 10:1:1, [ketone] = 0.1 M
RuCl
PPh3
NH2
(CH3)3Si
>99 10yield, %a <1
RuCl
ClNH2
(CH3)3SiSbF6
RuCl
CNt-C4H9
NH2
(CH3)3SiSbF6
PROPOSED MECHANISM
RuCl
ClNH2
baseRu
Cl NH
RuCl
LNH2
baseRu
Cl NH
SbF6
L
RuCl
HNH2
R
OH
R
O
H
+ +
– HSbF6
– HCl
– LL
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