This paper reports our investigations on the reactivity of a series of [Ni(diphosphine)2]2+ derivatives, including [Ni(PCy2NBz2)2](BF4)2, 1, with an atmosphere of carbon monoxide at room temperature. Complex 1 showed a unique ability to form a CO adduct under these conditions, and further characterization of this product has been carried out. A systematic study of the factors that favor formation of the CO adduct suggest that two bases in the second coordination sphere interact with the coordinated CO ligand to provide a stabilizing influence, and the generality of such an effect in this system is discussed. The effect of carbon monoxide on the catalytic activity of 1 for hydrogen oxidation has also been studied. D. L. D. acknowledges the support of the Office of Basic Energy Sciences of the Department of Energy, by the Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.
Revised: January 27, 2012 |
Published: January 23, 2008
Citation
Wilson A., A. Wilson, K. Fraze, K. Fraze, B. Twamley, S.M. Miller, and S.M. Miller, et al. 2008.The role of the second coordination sphere of [Ni(PCy2NBz2)2](BF4)2 in reversible carbon monoxide binding.Journal of the American Chemical Society 130, no. 3:1061-1068.PNNL-SA-56961.doi:10.1021/ja077328d