The bonding of cyanoethylenes to M(CO)5 (M = Cr, Mo, W) could lead to either olefin binding (via the C=C bond, or ?2) or nitrogen binding (?1). A recent report by Bubrin et al.1 indicate that the ?1 bonding mode is preferred over the ?2 mode in W(CO)5(C2(CN)4) counter to what had been previously reported. We have carried out computational (DFT) modeling of the ?1 and ?2 bonding for the full series of M(CO)5(C2Hn(CN)n) (M =Mo, W and n = 1 to 4) and found out that ?1 is preferred in all cases. Furthermore, the preference increases with an increase of the number of cyano substituents. We have also synthesized M(CO)5(E-C2H2(CN)2) and M(CO)5(C2(CN)4) (M = Mo, W) and measured their thermal decomposition kinetics. Experimental results agree with the computational predictions. Analyses of the aspects that govern the preference of ?1 bonding over ?2 bonding are discussed.1. Organometallics, 2012 , 31, 6305

Computational and experimental studies of cyanoethylene pentacarbonyl metal (molybdenum and tungsten) complexes: Insights into η<sup>2</sup> and η<sup>1</sup> competitive bonding

245th National Meeting (2013)

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Computational and experimental studies of cyanoethylene pentacarbonyl metal (molybdenum and tungsten) complexes: Insights into η2 and η1 competitive bonding

Computational and experimental studies of cyanoethylene pentacarbonyl metal (molybdenum and tungsten) complexes: Insights into η² and η¹ competitive bonding