作者:Zhang, Songshen、Shen, Jian Kun、Basolo, Fred、Ju, Telvin D.、Lang, Russell F.、Kiss, Gabor、Hoff, Carl D.
DOI:——
日期:——
Kinetics and mechanism of ligand substitution in [Cr(π-ligand)(CO)<sub>3</sub>] complexes (ligand = naphthalene, pyrene, thiophene, 2,6-dimethylpyridine, or cycloheptatriene) and of fac/mer isomerization in [M(CO)<sub>3</sub>L<sub>3</sub>](M = Cr, Mo or W; L = phosphite, phosphine or isocyanide)
作者:James A. S. Howell、Paul C. Yates、Neil F. Ashford、Denis T. Dixon、Richard Warren
DOI:10.1039/dt9960003959
日期:——
Kinetic studies of the reaction [Cr(pi-ligand)(CO)(3)] + 3L --> [Cr(CO)(3)L(3)] + pi-ligand revealed a second-order rate law with the pi-ligand lability decreasing in the order naphthalene > thiophene > cycloheptatriene > 2,5-dimethylpyridine. In terms of the entering ligand, the rates increased in the order PrCN < P(OMe)(3) < PBu(3). Rates of intramolecular exchange in the [M(CO)(6-x)P(OMe)(3)}(x)] series increased in the order x = 3 < 1 < 2 and M = Mo < W < Cr. These results are consistent with molecular modelling of the trigonal twist pathway for [Cr(CO)(6-x)(PR(3))(x)] complexes (x = 1-3, R = H or Me).