Abstract
Ab initio, generalized molecular orbital, configuration interaction calculations are reported for chromium-chromium quadruple bonds, for molybdenum-molybdenum triple bonds, and for niobium-carbon and molybdenum-carbon double bonds. The results for the potential energy curves of Cr-Cr quadruple bonds suggest that the nature of the bridging ligand is a major factor in determining the Cr-Cr bond distance. The predicted dissociation energy of the model molybdenum triple bond molecule, Mo2H6, is 284 kJ mol-1 . This value is at the lower range of the possible experimental values. The difference in the chemistry and bonding between the Fischer-type carbene, Mo(CO)5(C(OH)H), and the Schrock-type carbene, Nb(n -C5H5)C12(CH2), are shown to arise from the nature of the metal fragments. The Mo(CO)5 fragment with ligand stabilized π orbitals causes the carbene to be nucleophilic, while the NbCpC12 fragment with destabilized π orbitals causes the carbene to be electrophilic. The pivoting of the methylene in the electron deficient Nb complex is examined and involves both a rotation of the Nb-C bond and a direct Nb-H interaction.
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Hall, M.B. (1986). Multiple Metal-Metal and Metal-Carbon Bonds. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_28
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DOI: https://doi.org/10.1007/978-94-009-4656-9_28
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