Abstract
CASSCF and CCI calculations have been performed to analyze the bonding in Ni(C2H4)2. Three different relative orientations of the two olefins have been studied. It is found that a structure with D2d symmetry, where the C-C bonds in the two olefins make a 90 degree angle to each other, gives the lowest energy. A D2h form, with the two C-C bonds and Ni in the same plane, is 10.3 kcal/ mol higher in energy. The reason for the preference of the D2d form is analyzed in terms of valence bond theory, and is found to be due to a d 8 structure with two simultaneous d π bonds. A C 2v form, for which the two nickel olefin bonds make a 103 degree angle to each other and the C-C bonds are parallel to each other, is 32 kcal/mol higher in energy than the D2d form. The low binding energy of the C 2v form is due to a poor σ interaction with inefficient sd hybridization.
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Siegbahn, P.E.M., Brandemark, U.B. Orientational preference of two ethylene ligands bound to a nickel atom. Theoret. Chim. Acta 69, 119–133 (1986). https://doi.org/10.1007/BF00527684
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DOI: https://doi.org/10.1007/BF00527684