Bonding analysis and the mechanisms on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH

• Published in: Journal of organometallic chemistry Vol. 693; no. 4; pp. 639 - 645
• Main Authors: Bi, Siwei, Zhao, Yanyun, Kong, Xiaojian, Zhao, Xiaoran, Xie, Qingming
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-02-2008
• Subjects: Alkoxy-bridged bis(silylene) complex; Density functional calculation; Reaction mechanism; Ring-opening; Reaction mechanism; Density functional calculation; Alkoxy-bridged bis(silylene) complex; Ring-opening
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2007.11.044

The mechanistic study on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH is performed by using density functional theory.
The mechanistic study on the ring-opening of alkoxy-bridged bis(silylene) transition-metal complexes toward MeOH is performed by using density functional theory. Four steps are predicted to be involved in the reaction, formation of hydrogen bonding between
R and a MeOH, ring-opening of the Ru–Si1–O1–Si2 four-membered ring, formation of the six-membered ring, and the hydroxyl hydrogen migration to the metal center. It is found that the reaction is favorable thermodynamically and the hydroxyl hydrogen migration is the rate-determining step. Systematic variations of the structural parameters involved in the reaction mechanism are revealed, which revealed the relationship of the bond strength among Ru–Si, Si–O and O–H bonds.