Theoretical insights into the electronic structure of nickel(0)-diphosphine-carbon dioxide complexes

Kégl, Tímea R. and Carrilho, Rui M. B. and Kégl, Tamás (2020) Theoretical insights into the electronic structure of nickel(0)-diphosphine-carbon dioxide complexes. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 924. pp. 1-7. ISSN 0022-328X (print); 1872-8561 (online)

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Abstract

The coordination properties of carbon dioxide bound to Ni(0) with various phosphines have been inves- tigated by means of DFT calculations. Reasonable linear correlation has been found between Tolman’s electronic parameters (TEPs) and the asymmetric stretching frequency of the coordinated CO2. Two de- scriptors from EDA-NOCV calculations, namely the interaction energy and the Hirshfeld charge associated with the back donation component gave acceptable linear correlation as well with the TEPs. The coordination strength, as well as the C = O bond order in coordinated carbon dioxide can be tuned by varying the substituents on phosphorus: in the presence of electron withdrawing groups the C = O bond remains stronger and Ni-C interaction is weaker, moreover, a new Ni-O bond path is formed; whereas for more basic diphosphines the Ni –C bond order is higher and the coordinated carbon dioxide possess a weaker C = O bond.

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