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

Ramaraj, A and Reddy, K Hari Krishna and Keil, Helena and Herbst-Irmer, Regine and Stalke, Dietmar and Jemmis, Eluvathingal D and Jagirdar, Balaji R (2017) Approaches to Sigma Complexes via Displacement of Agostic Interactions: An Experimental and Theoretical Investigation. In: ORGANOMETALLICS, 36 (15). pp. 2736-2745.

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Abstract

A series of coordinatively unsaturated, 16-electron, cationic ruthenium complexes bearing PNP pincer ligands of the type RuH(L)((PNP)-P-R)](+) (L = PPh3, R = PhCH2 (3), Ph (4); L = CO, R = PhCH2 (5); (PNP)-P-R = 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 H-2, 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)((PNP)-P-R)](+) (L = PPh3, R = PhCH2 (3), Ph (4); L = CO, R = PhCH2 (5); (PNP)-P-R = RN(CH2CH2PPh2)(2)) complexes and the sigma-borane complex trans-RuH(CO)(eta(1)-H-BH2 center dot NMe3)((PNP)-P-R)](+) (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.

Item Type:	Journal Article
Publication:	ORGANOMETALLICS
Additional Information:	Copy right for this article belongs to the AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	09 Sep 2017 04:45
Last Modified:	09 Sep 2017 04:45
URI:	http://eprints.iisc.ac.in/id/eprint/57755

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