Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os3(CO)12 and Its Phosphine Substituted Derivatives

Chem. J. Chinese Universities ›› 1988, Vol. 9 ›› Issue (10): 1035.

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Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os₃(CO)₁₂ and Its Phosphine Substituted Derivatives

Shen Jiankun¹, Gao Yici¹, Shi Qizhen¹, Fred Basolo²

1. Department of Chemistry, Lanzhou University, Lanzhou;
2. Department of Chemistry, Northwestern University, Evanston, Hlinois 60201, U.S.A

Received:1987-04-28 Online:1988-10-24 Published:1988-10-24

Abstract

Abstract: Detailed kinetic data are reported for the reactions of COsubstitution of Os₃(CO)₁₂ and Os₃(CO)₁₁L (where L = PPh₃, AsPh₃, P(n-Bu)₃) in CH₂Cl₂-C₂H₅OH and CH₂Cl₂ respectively in the presence of Me₃NO. The results indicate that the reactions follow associative rate law, that is, r = k₂[complex][Me₃NO], and are independent of entering ligand concentration. The effect of C₂H₅OH as solvent on the reactions has been investigated quantitatively. Reaction mechanism, structures of transition states and intermediates have been proposed. The ligand effects on the reactions have been discussed as well.

Key words: Triosmium dodecacarbonyl, Trimethylamine N-Oxide, Oxygen atom transfer, Kinetics and mechanism

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Shen Jiankun, Gao Yici, Shi Qizhen, Fred Basolo. Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os₃(CO)₁₂ and Its Phosphine Substituted Derivatives[J]. Chem. J. Chinese Universities, 1988, 9(10): 1035.

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Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os₃(CO)₁₂ and Its Phosphine Substituted Derivatives

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