Half-Sandwich Ruthenium(II) Complexes of Click Generated 1,2,3-Triazole Based Organosulfur/-selenium Ligands: Structural and Donor Site Dependent Catalytic Oxidation and Transfer Hydrogenation Aspects

2013 ◽  
Vol 32 (13) ◽  
pp. 3595-3603 ◽  
Author(s):  
Fariha Saleem ◽  
Gyandshwar Kumar Rao ◽  
Arun Kumar ◽  
Goutam Mukherjee ◽  
Ajai K. Singh
Keyword(s):  
Catalytic Oxidation ◽  
Donor Site ◽  
Transfer Hydrogenation ◽  
Half Sandwich

scholarly journals New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2′-Bis(aminomethyl)-1,1′-binaphthyl

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1165
Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya
Keyword(s):  
Hydrogen Transfer ◽  
Bond Cleavage ◽  
Enantiomeric Excess ◽  
Transfer Hydrogenation ◽  
Catalyst Precursor ◽  
Asymmetric Catalysts ◽  
Axially Chiral ◽  
Diastereomeric Mixture ◽  
Raney Ni ◽  
Half Sandwich

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2′-bis(aminomethyl)-1,1′-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = η5–C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.

scholarly journals Quinone Reduction by Organo-Osmium Half-Sandwich Transfer Hydrogenation Catalysts

2021 ◽  
Vol 40 (17) ◽  
pp. 3012-3023
Author(s):  
Elizabeth M. Bolitho ◽  
Nathan G. Worby ◽  
James P. C. Coverdale ◽  
Juliusz A. Wolny ◽  
Volker Schünemann ◽  
...  
Keyword(s):  
Transfer Hydrogenation ◽  
Hydrogenation Catalysts ◽  
Quinone Reduction ◽  
Half Sandwich

Structure–activity relationship study of half-sandwich metal complexes in aqueous transfer hydrogenation catalysis

2020 ◽  
Vol 7 (3) ◽  
pp. 583-591 ◽  
Author(s):  
Anh H. Ngo ◽  
Loi H. Do
Keyword(s):  
Metal Complexes ◽  
Structure Activity Relationship ◽  
Transfer Hydrogenation ◽  
Activity Relationship ◽  
Structure Activity ◽  
Systematic Structure ◽  
Relationship Study ◽  
Hydrogenation Catalysis ◽  
Half Sandwich

A systematic structure–activity relationship study was performed to identify the factors that are important to enhancing the transfer hydrogenation efficiency of half-sandwich metal complexes.

Transfer Hydrogenation of Ketones Catalysed by New Half-Sandwich Ruthenium(II) Complexes Bearing the Sulfonated Phosphane (meta-Sulfonatophenyl)diphenylphosphane Potassium Salt (TPPMS)

2006 ◽  
Vol 2006 (14) ◽  
pp. 2855-2864 ◽  
Author(s):  
Josefina Díez ◽  
M. Pilar Gamasa ◽  
Elena Lastra ◽  
Almudena García-Fernández ◽  
M. Pilar Tarazona
Keyword(s):  
Potassium Salt ◽  
Transfer Hydrogenation ◽  
Half Sandwich
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