Does the Preferred Mechanism of a Catalytic Transformation Depend on the Density Functional? Ethylene Hydrosilylation by a Metal Complex as a Case Study

Wu, Yujie; Genest, Alexander; Rösch, Notker

doi:10.1021/jp5010677

Cited by 6 publications

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Imine hydrosilylation using an iron complex catalyst: A computational study

Dahy

Koga

2018

J Comput Chem

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The reaction mechanism for imine hydrosilylation in the presence of an iron methyl complex and hydrosilane was studied using density functional theory at the M06/6‐311G(d,p) level of theory. Benzylidenemethylamine (PhCH = NMe) and trimethylhydrosilane (HSiMe3) were employed as the model imine and hydrosilane, respectively. Hydrosilylation has been experimentally proposed to occur in two stages. In the first stage, the active catalyst (CpFe(CO)SiMe3, 1) is formed from the reaction of pre‐catalyst, CpFe(CO)2Me, and hydrosilane through CO migratory insertion into the FeMe bond and the reaction of the resulting acetyl complex intermediate with hydrosilane. In the second stage, 1 catalyzes the reaction of imine with hydrosilane. Calculations for the first stage showed that the most favorable pathway for CO insertion involved a spin state change, that is, two‐state reactivity mechanism through a triplet state intermediate, and the acetyl complex reaction with HSiMe3 follows a σ‐bond metathesis pathway. The calculations also showed that, in the catalytic cycle, the imine coordinates to 1 to form an FeCN three‐membered ring intermediate accompanied by silyl group migration. This intermediate then reacts with HSiMe3 to yield the hydrosilylated product through a σ‐bond metathesis and regenerate 1. The rate‐determining step in the catalytic cycle was the coordination of HSiMe3 to the three‐membered ring intermediate, with an activation energy of 23.1 kcal/mol. Imine hydrosilylation in the absence of an iron complex through a [2 + 2] cycloaddition mechanism requires much higher activation energies. © 2018 Wiley Periodicals, Inc.

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Imine hydrosilylation using an iron complex catalyst: A computational study

Dahy

Koga

2018

J Comput Chem

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Computational Approaches to Homogeneous Gold Catalysis

Faza

López

2014

Topics in Current Chemistry

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Homogenous gold catalysis has been exploding for the last decade at an outstanding pace. The best described reactivity of Au(I) and Au(III) species is based on gold's properties as a soft Lewis acid, but new reactivity patterns have recently emerged which further expand the range of transformations achievable using gold catalysis, with examples of dual gold activation, hydrogenation reactions, or Au(I)/Au(III) catalytic cycles.In this scenario, to develop fully all these new possibilities, the use of computational tools to understand at an atomistic level of detail the complete role of gold as a catalyst is unavoidable. In this work we aim to provide a comprehensive review of the available benchmark works on methodological options to study homogenous gold catalysis in the hope that this effort can help guide the choice of method in future mechanistic studies involving gold complexes. This is relevant because a representative number of current mechanistic studies still use methods which have been reported as inappropriate and dangerously inaccurate for this chemistry.Together with this, we describe a number of recent mechanistic studies where computational chemistry has provided relevant insights into non-conventional reaction paths, unexpected selectivities or novel reactivity, which illustrate the complexity behind gold-mediated organic chemistry.

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Catalytic Asymmetric trans-Selective Hydrosilylation of Bisalkynes to Access AIE and CPL-Active Silicon-Stereogenic Benzosiloles

Tang

Nie

et al. 2020

iScience

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Chirality widely exists in a diverse array of biologically active molecules and life forms, and the catalytic constructions of chiral molecules have triggered a heightened interest in the fields of chemistry and materials and pharmaceutical sciences. However, the synthesis of silicon-stereogenic organosilicon compounds is generally recognized as a much more difficult task than that of carbon-stereogenic centers because of no abundant organosilicon-based chiral sources in nature. Herein, we reported a highly enantioselective rhodium-catalyzed transselective hydrosilylation of silicon-tethered bisalkynes to access chiral benzosiloles bearing a silicon-stereogenic center. This protocol featured with chiral Ar-BINMOL-Phos bearing hydrogen-bond donors as a privileged P-ligand for catalytic asymmetric hydrosilylation that is operationally simple and has 100% atom-economy with good functional group tolerability as well as high enantioselectivity (up to >99:1 er). Benefiting from the trans-selective hydrosilylation with the aid of Rh/Ar-BINMOL-Phos-based asymmetric catalysis, the Si-stereogenic benzosiloles exhibited pronounced aggregation-induced emission (AIE) and circularly polarized luminescence (CPL) activity.

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Does the Preferred Mechanism of a Catalytic Transformation Depend on the Density Functional? Ethylene Hydrosilylation by a Metal Complex as a Case Study

Cited by 6 publications

References 50 publications

Imine hydrosilylation using an iron complex catalyst: A computational study

Imine hydrosilylation using an iron complex catalyst: A computational study

Computational Approaches to Homogeneous Gold Catalysis

Catalytic Asymmetric trans-Selective Hydrosilylation of Bisalkynes to Access AIE and CPL-Active Silicon-Stereogenic Benzosiloles

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