Markovnikov-Selective Hydrosilylation of Electron-Deficient Alkenes with Arylsilanes Catalyzed by Mono(phosphine)palladium(0)

Markovnikov-selective hydrosilylation of electron-deficient alkenes with HSiPh3 is catalyzed by a mono­(phosphine)­palladium(0) complex, Pd­(η2:η2-C6H10O)­(PMe3) (1a). The hydrosilylation of acrylonitrile with HSiPh3 at 30 °C proceeds to completion within 40 min in the presence of 5 mol % of 1a. The...

Full description

Saved in:
Bibliographic Details
Published inOrganometallics Vol. 34; no. 2; pp. 432 - 437
Main Authors Komine, Nobuyuki, Abe, Makoto, Suda, Ryoko, Hirano, Masafumi
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 26.01.2015
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
PALLADIUM
INSERTION
COMPLEXES
BONDS
PLATINUM
HOMOGENEOUS CATALYSIS
RECENT PROGRESS
HYDROSILATION
SILYLATION
Online AccessGet full text

Cover

More Information
Summary:Markovnikov-selective hydrosilylation of electron-deficient alkenes with HSiPh3 is catalyzed by a mono­(phosphine)­palladium(0) complex, Pd­(η2:η2-C6H10O)­(PMe3) (1a). The hydrosilylation of acrylonitrile with HSiPh3 at 30 °C proceeds to completion within 40 min in the presence of 5 mol % of 1a. The complex 1a also shows the catalytic activity for the hydrosilylation with mono- and diarylsilanes and monochlorosilane such as HSiPhMe2, HSiPh2Me, and HSiClMe2. The hydrosilylation using para-substituted styrenes clearly shows the electron-withdrawing substituent promoting the reaction. Mechanistic studies indicate that the reaction is proceeding by a Chalk–Harrod mechanism with the reductive elimination of an (alkyl)­(silyl)­palladium­(II) intermediate being the rate-determining step.
Bibliography:KAKEN
ISSN:0276-7333
1520-6041
DOI:10.1021/om500964g