Kinetics and mechanism of the outer-sphere oxidation of metal carbonyl anions with coordination complexes containing chloride

Journal Article · Sat Feb 01 04:00:00 EST 1992 · Organometallics

DOI:https://doi.org/10.1021/om00038a013· OSTI ID:555003

Lai, C K; Corraine, M S; Atwood, J D ^[1]

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1. State Univ. of New York, Buffalo, NY (United States)

Reactions of metal carbonyl anions, CpFe(CO){sub 2}{sup -}, Re(CO){sub 5}{sup -}, Mn(CO){sub 5}{sup -}, CpMo(CO){sub 3}{sup -}, CpCr(CO){sub 3}{sup -}, and Co(CO){sub 4}{sup -}, with CrCl{sub 3}{center_dot}3S (S = THF, CH{sub 3}CN) and reactions of Mn(CO){sub 5}{sup -} and Re(CO){sub 5}{sup -} with [Co(o-phen){sub 2}Cl{sub 2}]CIO{sub 4} are reported. Net oxidation/reduction chemistry is observed with formation of metal carbonyl dimers and CrCl{sub 2}{center_dot}4S or Co(o-phen){sub 2}Cl{sub 2}. Metal carbonyl halides are also observed and shown to arise from a secondary reaction of the metal carbonyl dimer with the oxidant. The products and rates are most consistent with outer-sphere electron-transfer reactions. Reactions of CpFe(CO){sub 2}{sup -} with CpFe(CO){sub 2}X (X = Cl, Br, I) are also reported. The rate dependence on X is very small and in the order expected for nucleophilic substitution. 21 refs. 1 fig., 4 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 555003
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 2 Vol. 11; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ANIONS
BROMINE COMPOUNDS
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM CHLORIDES
CHROMIUM COMPOUNDS
DIMERS
ELECTRON TRANSFER
HALIDES
IODINE COMPOUNDS
IRON COMPOUNDS
MOLYBDENUM COMPOUNDS
OXIDATION
RHENIUM COMPOUNDS