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Kinetics and mechanism of the reactions of di-μ-carbonyl-bis(cyclopentadienyl)dinickel(0) with monodentate ligands
Ellgen, Paul C.
, p. 232 - 239 (2008/10/08)
The ligands carbon monoxide, triphenylarsine, triphenyl phosphite, triphenylphosphine, ethyldiphenylphosphine, and tri-n-butylphosphine react with di-μ-carbonyl-bis(cyclopentadienyl)dinickel(0) to give nickelocene and diliganddicarbonylnickel(0) (eq 1). The kinetics of these reactions have been studied by following the carbonyl region infrared spectra of reaction mixtures or by manometric observation of carbon monoxide absorption. Complicated behavior is observed with tri-n-butylphosphine. The dependence on carbon monoxide concentration was not studied, but reaction according to (1) is much slower than the rate reported for carbon monoxide exchange. For the other ligands studied, a second-order rate law, first order in each reactant, is observed: -d[Ni2(CO)2(C5H5)2]/dt = k[Ni2(CO)2(C5H5)2][L]. The reaction mechanism is discussed. A complex mechanism can be shown to be quantitatively consistent with the data for the reaction with tri-n-butylphosphine.
