Alkyne insertion into the Ru-C bond of a four-membered metallacycle. Insertion rate and reaction pathway

Ghosh, Kaushik ; Chattopadhyay, Swarup ; Pattanayak, Sujay ; Chakravorty, Animesh (2001) Alkyne insertion into the Ru-C bond of a four-membered metallacycle. Insertion rate and reaction pathway Organometallics, 20 (7). pp. 1419-1423. ISSN 0276-7333

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Official URL: http://pubs.acs.org/doi/abs/10.1021/om000649c

Related URL: http://dx.doi.org/10.1021/om000649c

Abstract

The insertion of HOCH2CCH (ha) into the Ru-C bond of RuII(RL1)(PPh3)2(CO)Cl, 1, has afforded RuII(RL3)(PPh3)2(CO)Cl, 3, which has been structurally characterized. Insertion rates in CH2Cl2-MeOH for ha as well as for PhCCH (pa), which inserts similarly into 1 affording RuII(RL2)(PPh3)2(CO)Cl, 2, are proportional to the product of the concentrations of alkyne and methanol. The insertion rate of ha is nearly 5 times faster than that of pa, and for a given alkyne the rate increases as R becomes more electron-withdrawing (OMe < Me < Cl). A reaction model implicating the adduct 1·MeOH, which binds and activates the alkyne via displacement of MeOH, is proposed.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:6775
Deposited On:22 Oct 2010 06:45
Last Modified:31 Jan 2011 06:00

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