INFRARED AND KINETIC STUDIES OF GROUP-VI METAL PENTACARBONYL AMINE COMPOUNDS uri icon

abstract

  • Compounds of the type M(CO)5amine, where M = Cr, Mo, and W, undergo thermal decomposition reactions to form M(CO)6 reaction products. The rate of reaction follows the first-order rate law: rate = k1[M(CO)5amine]. The rate constant k1, for a particular metal, was found to decrease as the pKa of the amine increased. This is consistent with the proposed dissociative mechanism which involves a cleavage of the metal-nitrogen bond in the rate-determining step. Compounds containing unsaturated amine ligands, such as pyridines, were observed to be much more stable than their pKa values would indicate. This is interpreted as resulting from a small amount of metal-nitrogen back-bonding. No correlation was observed between the nature of the metal-nitrogen bond, as indicated by the rate constant (k1) or pKa for the amine group, and the calculated CO stretching force constants. 1972, American Chemical Society. All rights reserved.

published proceedings

  • INORGANIC CHEMISTRY

altmetric score

  • 3

author list (cited authors)

  • DENNENBERG, R. J., & DARENSBOURG, D. J.

citation count

  • 78

complete list of authors

  • DENNENBERG, RJ||DARENSBOURG, DJ

publication date

  • January 1972