# The Remarkable Nb_{2}(CO)_{12} with Seven-Coordinate Niobium: Decarbonylation to Nb_{2}(CO)_{11} and Nb_{2}(CO)_{10}

journal contribution

posted on 12.07.2011, 00:00 by Lihong Tang, Qiong Luo, Qian-shu Li, Yaoming Xie, R. Bruce King, Henry F. SchaeferThe dissociation of Nb

_{2}(CO)_{12}into two Nb(CO)_{6}units is predicted to require ∼13 kcal/mol so that Nb_{2}(CO)_{12}rather than Nb(CO)_{6}is the anticipated initial oxidation product of the known Nb(CO)_{6}^{–}anion. This differs from the corresponding vanadium carbonyl chemistry where V(CO)_{6}rather than V_{2}(CO)_{12}is found experimentally to be the oxidation product of V(CO)_{6}^{–}. The lowest energy Nb_{2}(CO)_{12}structure consists of two Nb(CO)_{6}fragments joined by a Nb–Nb bond of ∼3.4 Å length so that each niobium atom is heptacoordinate, counting the metal–metal bond. These niobium coordination polyhedra can be approximated by capped octahedra. Among unsaturated binuclear niobium carbonyls the lowest energy Nb_{2}(CO)_{11}structure has a formal four-electron donor bridging η^{2}-μ-CO group and a formal Nb–Nb single bond rather than only two-electron donor carbonyl groups and a formal NbNb double bond. The Nb_{2}(CO)_{11}structures with formal NbNb double bonds and exclusively two-electron donor carbonyl groups lie more than 13 kcal/mol above this low-energy Nb_{2}(CO)_{10}(η^{2}-μ-CO) structure. However, Nb_{2}(CO)_{11}is predicted to be thermodynamically disfavored, owing to disproportionation into Nb_{2}(CO)_{12}+ Nb_{2}(CO)_{10}, a slightly exothermic process by ∼4 kcal/mol. The Nb_{2}(CO)_{10}structures with formal NbNb triple bonds and all two-electron donor carbonyl groups appear to be particularly favorable, as suggested by high CO dissociation energies and viability toward disproportionation. Such structures are isolobal with Cp_{2}Mo_{2}(CO)_{4}, which was the first stable metal carbonyl to be discovered with a short metal–metal distance, corresponding to a formal triple bond. Considerably higher energy Nb_{2}(CO)_{10}structures (by more than 20 kcal/mol) have two four-electron donor bridging carbonyl groups and long niobium–niobium distances. Such structures can be considered to consist of a bidentate Nb(CO)_{6}“ligand” coordinating to a Nb(CO)_{4}unit through the two η^{2}-μ-CO groups.