Cationic silane sigma-complexes of ruthenium with relevance to catalysis.

Hydrosilylation of carbonyls catalyzed by 2 goes via intermediate formation of cationic silane sigma-complexes 4 which undergo nucleophilic abstraction of the silylium cation studied by DFT calculations.

[1]  D. Gutsulyak,et al.  Steric and Electronic Effects in Half-Sandwich Ruthenium Silane σ-Complexes with Si−H and Si−Cl Interligand Interactions† , 2009 .

[2]  M. Abu‐Omar,et al.  Catalysis by cationic oxorhenium(v): hydrolysis and alcoholysis of organic silanes. , 2009, Dalton transactions.

[3]  M. Brookhart,et al.  Reduction of Alkyl Halides by Triethylsilane Based on a Cationic Iridium Bis(phosphinite) Pincer Catalyst: Scope, Selectivity and Mechanism , 2009 .

[4]  P. White,et al.  Scope and mechanism of the iridium-catalyzed cleavage of alkyl ethers with triethylsilane. , 2008, Journal of the American Chemical Society.

[5]  P. White,et al.  Structural and spectroscopic characterization of an unprecedented cationic transition-metal eta1-silane complex. , 2008, Angewandte Chemie.

[6]  D. Gutsulyak,et al.  Cp(Pri2MeP)FeH2SiR3: nonclassical iron silyl dihydride. , 2008, Journal of the American Chemical Society.

[7]  G. Du,et al.  Mechanistic insight into hydrosilylation reactions catalyzed by high valent ReX (X = O, NAr, or N) complexes: the silane (Si-H) does not add across the metal-ligand multiple bond. , 2007, Journal of the American Chemical Society.

[8]  K. McNeill,et al.  Catalytic Dehalogenation of sp2 C−F and C−Cl Bonds in Fluoro- and Chloroalkenes , 2006 .

[9]  A. Bell,et al.  Stoichiometric and Catalytic Reactions Involving Si-H Bond Activations by Rh and Ir Complexes Containing a Pyridylindolide Ligand , 2006 .

[10]  M. Abu‐Omar,et al.  Hydrogen production from hydrolytic oxidation of organosilanes using a cationic oxorhenium catalyst. , 2005, Journal of the American Chemical Society.

[11]  O. Ozerov,et al.  Room-temperature catalytic hydrodefluorination of C(sp3)-F bonds. , 2005, Journal of the American Chemical Society.

[12]  G. Nikonov.  Recent Advances in Nonclassical Interligand Si…H Interactions , 2005 .

[13]  O. Riant,et al.  Recent advances in the asymmetric hydrosilylation of ketones, imines and electrophilic double bonds , 2004 .

[14]  Stuart R. Dubberley,et al.  Nonclassical titanocene silyl hydrides. , 2004, Chemistry.

[15]  I. Ojima.  The Hydrosilylation Reaction , 2004 .

[16]  Miguel A. Esteruelas,et al.  Dehalogenation of Hexachlorocyclohexanes and Simultaneous Chlorination of Triethylsilane Catalyzed by Rhodium and Ruthenium Complexes , 2004 .

[17]  G. Kubas.  HETEROLYTIC SPLITTING OF HH, SiH, AND OTHER σ BONDS ON ELECTROPHILIC METAL CENTERS , 2004 .

[18]  R. Bullock,et al.  A recyclable catalyst that precipitates at the end of the reaction , 2003, Nature.

[19]  M. Bühl,et al.  Density functional study of catalytic silane alcoholysis at a [Fe(Cp)(CO)(PR3)]+ center , 2003 .

[20]  P. Markwick,et al.  Dynamic effects on j-couplings across hydrogen bonds in proteins. , 2003, Journal of the American Chemical Society.

[21]  B. Chaudret,et al.  Mechanistic studies on ethylene silylation with chlorosilanes catalysed by ruthenium complexes. , 2003, Chemical communications.

[22]  Jean-François Carpentier and Virginie Bette.  Chemo- and Enantioselective Hydrosilylation of Carbonyl and Imino Groups. An Emphasis on Non-Traditional Catalyst Systems , 2002 .

[23]  Zhenyang Lin,et al.  Structural and bonding characteristics in transition metal-silane complexes. , 2002, Chemical Society reviews.

[24]  L. Brammer,et al.  [Cp(PMe3)2Ru(η2-HSiCl3)]+: Structure and Bonding of a Rare Cationic η2-Silane Complex , 2002 .

[25]  Mamoru Igarashi,et al.  Ruthenium complex catalyzed hydrosilylation of esters: a facile transformation of esters to alkyl silyl acetals and aldehydes , 2001 .

[26]  B. Scott,et al.  H2 binding to and silane alcoholysis on an electrophilic Mn(I) fragment with tied-back phosphite ligands. X-ray structure of a Mn–CH2Cl2 complex , 2000 .

[27]  B. Scott,et al.  Synthesis of and Small Molecule Coordination to Highly Electrophilic Cationic Manganese(I) and Rhenium(I) Carbonyl Complexes with Tied-Back Phosphites , 2000 .

[28]  Gevorgyan,et al.  A novel B(C(6)F(5))(3)-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes , 2000, The Journal of organic chemistry.

[29]  Piers,et al.  Studies on the mechanism of B(C(6)F(5))(3)-catalyzed hydrosilation of carbonyl functions , 2000, The Journal of organic chemistry.

[30]  B. Scott,et al.  Reactions of H2, silanes, and olefins with superelectrophilic cationic rhenium complexes: heterolytic cleavage of H2 and relation to the structure and function of hydrogenases , 1999 .

[31]  J. Y. Corey,et al.  Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds. , 1999, Chemical reviews.

[32]  W. Piers,et al.  Tris(pentafluorophenyl)boron-Catalyzed Hydrosilation of Aromatic Aldehydes, Ketones, and Esters , 1996 .

[33]  M. Brookhart,et al.  SPECTROSCOPIC CHARACTERIZATION AND DYNAMIC PROPERTIES OF CATIONIC ETA 2-SILANE AND ETA 2-H2 COMPLEXES OF GENERAL STRUCTURE CP(CO)(L)FE(HSIR3)+ AND CP( CO)(L)FE(H2)+ (L=PET3, PPH3) , 1995 .

[34]  B. T. Gregg,et al.  Catalytic hydrosilylation of organic esters using manganese carbonyl acetyl complexes. , 1995 .

[35]  R. Crabtree.  Transition Metal Complexation of σ Bonds , 1993 .

[36]  S. Buchwald,et al.  An air-stable catalyst system for the conversion of esters to alcohols , 1992 .

[37]  R. Eisenberg,et al.  Dehydrogenative coupling reactions to form silazane oligomers promoted by binuclear rhodium complexes , 1991 .

[38]  S. Buchwald,et al.  A catalytic method for the reduction of esters to alcohols , 1991 .

[39]  R. Crabtree,et al.  Homogeneous catalysis of silane alcoholysis via nucleophilic attack by the alcohol on an Ir(.eta.2-HSiR3) intermediate catalyzed by [IrH2S2(PPh3)2]SbF6 (S = solvent) , 1989 .

[40]  R. Laine,et al.  Catalytic Synthesis of Oligosilazanes. 2 , 1988 .

[41]  R. Laine,et al.  Catalytic methods for the synthesis of oligosilazanes , 1986 .

[42]  I. Ojima,et al.  REDUCTION OF CARBONYL COMPOUNDS VIA HYDROSILYLATION. 3. ASYMMETRIC REDUCTION OF KETO ESTERS VIA HYDROSILYLATION CATALYZED BY A RHODIUM COMPLEX WITH CHIRAL PHOSPHINE LIGANDS , 1976 .

[43]  I. Ojima,et al.  A CONVENIENT ROUTE TO AMINOSILANES USING HYDROSILANE-RHODIUM(I) COMPLEX COMBINATIONS , 1973 .