Theoretical investigation on possible mechanisms on regioselective formation of (η3-siloxyallyl)tungsten complexes

Bi, Siwei; Liu, Yuxia; Chen, Guang; Zhang, Lisheng; Sun, Min; Li, Ping

doi:10.1016/j.jorganchem.2009.06.029

Cited by 3 publications

(1 citation statement)

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“…It was found that MeCN is sterically less hindered and has a poorer electrophilic cyanide carbon center, and thus cyanide insertion into a tungsten–silyl bond (formed via hydride migration from the metal center to the silylene Si center) was experimentally observed. Theoretical calculations have also been performed to explore the reaction mechanism between the tungsten silylene hydride complex and α,β-unsaturated carbonyl compounds . The results indicated that the favorable reaction pathway corresponds to [2 π + 4 π ] conjugate cycloaddition followed by Si–H reductive elimination.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Reactivity Difference of Isocyanate and Isothiocyanate toward a Ruthenium Silylene Hydride Complex

Lin

2014

Organometallics

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The detailed reaction mechanisms of the CO hydrosilylation of isocyanate and the CS bond cleavage of isothiocyanate mediated by the neutral ruthenium silylene hydride complex Cp*(CO)(H)RuSi(H){C(SiMe 3 ) 3 } have been investigated with the aid of density functional theory calculations. Through the investigation, the difference in reactivity between isocyanate and isothiocyanate toward the ruthenium silylene hydride complex has been examined and discussed. The different bond strengths and π-accepting abilities of CO and CS and the different degrees of affinity of O and S toward the Si center in the silylene ligand contribute to the different reactivities of the isocyanate and isothiocyanate substrates observed experimentally.

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Section: Introductionmentioning

confidence: 99%