Organometallics
Organometallics
5 years ago

Approaches to Sigma Complexes via Displacement of Agostic Interactions: An Experimental and Theoretical Investigation

Approaches to Sigma Complexes via Displacement of Agostic Interactions: An Experimental and Theoretical Investigation
Dietmar Stalke, Regine Herbst-Irmer, Eluvathingal D. Jemmis, K. Hari Krishna Reddy, Balaji R. Jagirdar, Helena Keil, A. Ramaraj
A series of coordinatively unsaturated, 16-electron, cationic ruthenium complexes bearing PNP pincer ligands of the type [RuH(L)(PNRP)]+ (L = PPh3, R = PhCH2 (3), Ph (4); L = CO, R = PhCH2 (5); PNRP = RN(CH2CH2PPh2)2) has been prepared and characterized. These complexes exhibit agostic interaction in the sixth coordination site. The binding of various X–H (X = H, Si, B, and C) bonds in small molecules such as H2, silanes, tetracoordinate boranes, and CH4 to the ruthenium center via displacement of the relatively weak agostic interaction in these complexes has been studied. Structures of [RuH(L)(PNRP)]+ (L = PPh3, R = PhCH2 (3), Ph (4); L = CO, R = PhCH2 (5); PNRP = RN(CH2CH2PPh2)2) complexes and the sigma-borane complex trans-[RuH(CO)(η1-H-BH2·NMe3)(PNRP)]+ (R = PhCH2 (15)) have been established by X-ray crystallography. The relative binding strengths of the X–H bonds to ruthenium center in these complexes has been studied using computational methods.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00210

DOI: 10.1021/acs.organomet.7b00210

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