Organometallics p. 1703 - 1706 (1986)
Update date:2022-08-04
Topics:
Turaki, Natalyia N.
Huggins, John M.
The substitution reactions of the CpW(CO)3 radical with phosphines and phosphites have been studied by using a competition experiment. Reaction of CpW(CO)3H with Ph3C in the presence of Ph3CCl and the ligand gave CpW(CO)3Cl (2) and CpW(CO)2(PR3)Cl (3) as the only metal-containing products. Plots of 3/2 vs. [PR3] were found to be linear with zero intercepts. The reactivity order PBu3 > P(OPh)3 > PPh3 was observed, and substitution was significantly inhibited by CO. Furthermore plots of 3/2 vs. 1/[Ph3CCl] at constant ligand concentration were found to be linear under nitrogen, but [Ph3CCl] independent under CO. These results were interpreted in terms of an associative substitution pathway.
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