Elsevier

Chemical Physics Letters

Volume 185, Issues 5–6, 25 October 1991, Pages 522-528
Chemical Physics Letters

On the relative stability of side-on and end-on coordination of dinitrogen to nickel (O): ”ab initio“ calculations on the model compounds [NiN2] and [Ni(PH3)2N2]

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Abstract

”Ab initio“ calculations have been performed on the systems NiN2 and Ni(PH3)2N2 to investigate the relative stability of end-on and side-on coordination of dinitrogen to Ni0. The results indicate that both the π-back-donation and the reduction in the σ repulsion are important factors in the description of the NiN2 bonding. In NiN2, it is possible to reduce efficiently the repulsion by 4s polarization and the dinitrogen can come close enough to nickel in order to reach overlap in the π space for end-on coordination: this favors the end-on bonding with respect to the side-on one. When ligands are present on both sides of nickel, 4s polarization is no loger possible and N2 cannot come close enough to nickel to allow the best overlap: this disfavors mainly the end-on coordination where a shorter r(NiN) is required and explains the preference for side-on coordination in Ni(PH3)2N2.

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