Oxidative Addition of Silicon-Chloride Bonds to a Zerovalent Ruthenium Center and Direct Generation of an Ethylene Insertion Complex

Hyojong Yoo; Donald H Berry

doi:10.1021/acs.inorgchem.2c01317

Oxidative Addition of Silicon-Chloride Bonds to a Zerovalent Ruthenium Center and Direct Generation of an Ethylene Insertion Complex

Inorg Chem. 2022 Jun 13;61(23):8639-8643. doi: 10.1021/acs.inorgchem.2c01317. Epub 2022 May 31.

Authors

Hyojong Yoo¹, Donald H Berry²

Affiliations

¹ Department of Materials Science and Chemical Engineering, Hanyang University, Ansan-si, Gyeonggi-do 15588, Republic of Korea.
² Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.

PMID: 35639447
DOI: 10.1021/acs.inorgchem.2c01317

Abstract

The oxidative addition of a silicon-chloride (Si-Cl) bond to a metal center can be a key reaction step in coordinative silicon chemistry, but this reaction is seldom observed. Herein, we report direct oxidative addition of the Si-Cl bonds of dimethyldichlorosilane (Me₂SiCl₂) and cyclotrimethylenedichlorosilane [(CH₂)₃SiCl₂] to low-valent ruthenium complexes, yielding the 16e^- chloro(organosilyl)ruthenium complexes [N₃]Ru(Cl)(SiMe₂Cl) (4a) and [N₃]Ru(Cl)(SiCl(CH₂)₃) (4b) ([N₃] = 2,6-(MesN═CMe)₂C₅H₃N; Mes = 1,3,5-trimethylphenyl; Me = methyl). The reversible reaction of 4a with ethylene yields an 18e^- ethylene adduct, in which an ethylene is subsequently inserted into a ruthenium-silicon (Ru-Si) bond to produce the 16e^- complex [N₃]Ru(Cl)(CH₂CH₂SiMe₂Cl) (7). This study provides a good example of the direct generation of an ethylene insertion product, which is an important intermediate in the catalytic reduction of unsaturated molecules.