Title: Steric and Electronic Effects in Linkage Isomerization Reactions of M(CO)<sub>5</sub>(L) (M = Cr, Mo, W; L = 2-methyl-2,3-dihydrofuran, 2,3-dihydropyran)
Abstract: Time-resolved infrared absorption spectroscopy is used to investigate the kinetics of the linkage isomerization reaction M(CO)5(η1-L) → M(CO)5(η2-L), where M = Cr, Mo, or W, and L = 2-methyl-2,3-dihydrofuran or 2,3-dihydropyran. Photolysis of M(CO)6 in cyclohexane in the presence of excess L produces the η1 (O-bound) isomer as the sole kinetic product. The kinetic product subsequently reacts intramolecularly to form an equilibrium mixture of the η1 and η2 (CC bound) isomers. Activation and equilibrium parameters are derived for the reactions and compared with previous results for linkage isomerization of the M(CO)5(dihydrofuran) complexes. The results of the experimental study, supported by DFT calculations, indicate that for M = W the kinetics of the η1 → η2 isomerization depend primarily on how close the double bond is to the metal atom in the η1 isomer, while the thermodynamics of the η1 ⇄ η2 equilibrium are determined primarily by electronic factors. In contrast, for M = Cr and Mo, both steric and electronic factors play a role in the isomerization kinetics.
Publication Year: 2007
Publication Date: 2007-08-23
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 7
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