Ruthenium based catalysts for olefin hydrosilylation: dichloro(p-cymene)ruthenium and related complexes.

  title={Ruthenium based catalysts for olefin hydrosilylation: dichloro(p-cymene)ruthenium and related complexes.},
  author={Tell Tuttle and Dongqi Wang and Walter Thiel and Jutta E. H. K{\"o}hler and Marco Hofmann and Johann Weis},
  journal={Dalton transactions},
We report our third and final investigation into the use of ruthenium based compounds for catalyzing the hydrosilylation of methylvinyldimethoxysilane with methyldimethoxysilane. The catalytic mechanism of dichloro(p-cymene)ruthenium(II) (B1) is examined and compared to that of previously studied, less active catalysts. Density functional theory (DFT) has been applied to explore the possibility of fine-tuning the catalytic ability of B1. The eta(6)-ligand and the sigma-donor ligands were varied… Expand
17 Citations
Olefin Hydrosilylation Catalyzed by a Bis-N-Heterocyclic Carbene Rhodium Complex. A Density Functional Theory Study
Using a density functional theory method, we explored four reaction mechanisms of hydrosilylation of silane and ethylene as model substrates, catalyzed by a Rh(I) complex with a bidendateExpand
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Theoretical studies combined with experimental evidence confirm that steric effect plays a critical role in governing the regio- and stereoselectivity, and the interplay between the substituent in the alkyne and the ligand ultimately determines the observed remarkable regio - and stereodivergence. Expand
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The mechanism of carbonyl hydrosilylation by cationic cyclopentadienyl molybdenum/tungsten complexes, [CpM(CO)2(IMes)]+ (M = Mo, W), has been investigated using density functional calculations.Expand
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The catalytic activity in the hydrosilylation of terminal alkynes by the unsaturated hydrido iridium(III) compound [IrH(κ3-hqca)(coe)] (1), which contains the rigid asymmetrical dianionic ONO pincerExpand
New Insights into Mechanism of Molybdenum(VI)-Dioxo Complex Catalyzed Hydrosilylation of Carbonyls: An Alternative Model for Activating Si-H Bond.
MoO2Cl2 behaves similar to Lewis acidic trispentafluorophenyl borane B(C6F5)3 in activating Si-H bond and is calculated to be ∼10.0 kcal/mol lower than the previously proposed [2 + 2] addition pathway for a variety of silanes and aldehyde/ketone substrates. Expand
Ruthenium catalyzed selective hydrosilylation of aldehydes.
A chemoselective hydrosilylation method for aldehydes is developed using a ruthenium catalyst and the proposed catalytic cycle involves a 1,3-hydride migration. Expand
Sequential Catalysis for the Production of Sterically Hindered Amines: Ru(II)-Catalyzed C–H Bond Activation and Hydrosilylation of Imines
Sequential ruthenium(II) catalyzed reactions for the production of secondary amines from simple imines are reported. They involve Ru(II)-acetate based catalytic systems for C–H BondExpand
Recent Advances in Transition-Metal-Catalyzed Synthetic Transformations of Organosilicon Reagents
Organosilicon compounds act as a nucleophile upon activation by an appropriate base and behave in a manner similar to main-group organometallic reagents. In the last decades, structurally divergentExpand
Highly Regio- and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions.
The sulfenyl group in the substrates was found to provide important chelation stabilization to direct the reaction through a new mechanistic pathway and provided important insight into the mechanism, particularly the unusual syn selectivity with the [Cp*Ru(MeCN)3 ](+) catalyst. Expand


Mechanism of olefin hydrosilylation catalyzed by ruCI2(CO)2(PPh3)2
Density functional theory (DFT) was used to explore the different mechanistic possibilities for the hydrosilylation reaction between methyldimethoxysilane and methylvinyldimethoxysilane catalyzed byExpand
Mechanism of olefin hydrosilylation catalyzed by [RuCl(NCCH3)5]+: A DFT study
Density functional theory (DFT) was used to explore the different mechanistic possibilities for the hydrosilylation reaction between methyldimethoxysilane and methylvinyldimethoxysilane catalyzed byExpand
Mechanism of olefin metathesis with catalysis by ruthenium carbene complexes: density functional studies on model systems.
Comparisons with experiment indicate that steric effects must also be considered for real catalysts containing bulky substituents when rationalizing in terms of electronic effects. Expand
The reactions of hydrosilanes with trifluoropropene and pentafluorostyrene catalyzed by ruthenium, rhodium and palladium complexes
Abstract The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru3(CO)12 or RhCl(PPh3)3 give β-Rf-vinylsilane (1) and/or β-Rf-ethylsilane (2) (Rf =Expand
Why Does the Rhodium-Catalyzed Hydrosilylation of Alkenes Take Place through a Modified Chalk−Harrod Mechanism? A Theoretical Study
Rh-catalyzed hydrosilylation of ethylene was theoretically investigated with the DFT, MP4(SDQ), and CCSD(T) methods, where RhCl(PH3)3 was adopted as a model catalyst. The rate-determining step in theExpand
Hydrosilylation with Bis(alkynyl)(1,5-cyclooctadiene)platinum Catalysts: A Density Functional Study of the Initial Activation
At elevated temperatures bis(alkynyl)(1,5-cyclooctadiene)platinum complexes catalyze the cross-linking of polyorganosiloxanes containing Si−H and vinyl groups. Density functional calculations withExpand
Pentacarbonyliron(0) Photocatalyzed Reactions of Trialkylsilanes with Alkenes.
Abstract We report results of the near-ultraviolet irradiation of Fe(CO) 5 in the presence of R 3 SiH (R  Me or Et) and an alkene. Good conversion to a mixture of alkane, (alkyl)SiR 3 , andExpand
Mechanistic Study of Ruthenium-Catalyzed Hydrosilation of 1-(Trimethylsilyl)-1-buten-3-yne
Catalytic hydrosilation of 1-(trimethylsilyl)-1-buten-3-yne (1) with three kinds of hydrosilanes (HSiMePh2, HSiMe2Ph, and HSiEt3) in CDCl3 at 30 °C in the presence of a catalytic amount ofExpand
Intramolecular endo-dig hydrosilylation catalyzed by ruthenium: evidence for a new mechanistic pathway.
  • B. Trost, Z. Ball
  • Chemistry, Medicine
  • Journal of the American Chemical Society
  • 2003
The ruthenium catalyst [Cp*Ru(MeCN)3]PF6 effects a novel intramolecular hydrosilylation of homo- and bis-homopropargylic alcohols, producing products of unique regioselectivity under very mild conditions with excellent selectivity, implying the necessity for a reexamination of the mechanism surrounding trans-hydrosallylation reactions. Expand
Addition of Catecholborane to a Ruthenium-Alkyl: Evidence for .sigma.-Bond Metathesis with a Low-Valent, Late Transition Metal
Addition of catecholborane to the low-valent CpRu(PPh 3 ) 2 Me complex led to formation of the corresponding ruthenium hydride and methylcatecholborane by a mechanism more characteristic ofExpand