Electronic and steric effects on the rate of oxidative addition of methyl iodide to diaryl(2,2′-bipyridyl)platinum(II) complexes
Abstract
The rates of oxidative addition of methyl iodide to the comolexes [PtR2(bipy)][bipy = 2,2′-bipyridyl; R = Me, Ph, 4-XC6H4(X = F, Cl, Me, or OMe), and 3-XC6H4(X = F or OMe) have been studied.
The second-order rate constants follow the series R = Me > 4-MeOC6H4 > 4-MeC6H4 > 3-MeOC6H4 > Ph > 4-FC6H4 > 4-ClC6H4 > 3-FC6H4, and can be correlated with the energy of a metal-to-ligand charge-transfer transition in the electronic spectra of the platinum(II) complexes. The complexes [Pt(4-CF3C6H4),(bipy)] and [Pt(2-MeC6H4)2(bipy)] fail to react with methyl iodide, in the former case due to electronic effects of the CF3 group and in the latter case due to steric hindrance by the methyl substituents.
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