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Issue 6, 1988
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Allylation of cobalt-co-ordinated cyclo-octatetraene by the [Fe{P(OMe)3}(NO)23-allyl)]+ cation: ring closure to 1,2,3,3a-tetrahydropentalenyl derivatives and the X-ray structure of [Co(η5-C8H8R)(η-C5Me5)][PF6][R = CH2C(Me)[double bond, length half m-dash]CH2]

Abstract

The reaction of [Fe{P(OMe)3}(NO)23-allyl)][PF6][1; allyl = CH2CHCH2, CH2CHCHMe, or CH2C(Me)CH2] with [Co(η4-cot)(η-C5R′5)](2; R′= H or Me, cot = cyclo-octatetraene) results in C–C coupling and the formation of 1,2,3,3a-tetrahydropentalenyl derivatives [Co(η5-C8H8R)(η-C5R′5)][PF6][3; R = CH2CH[double bond, length half m-dash]CH2, CH2CH[double bond, length half m-dash]CHMe, or CH2C(Me)[double bond, length half m-dash]CH2; R′= H or Me]. An X-ray diffraction study on [Co(η5-C8H8R)(η-C5Me5)][PF6][R = CH2C(Me)[double bond, length half m-dash]CH2] confirms the structure assignment with the cobalt atom co-ordinated to an η5-1,2,3,3a-tetrahydropentalenyl ligand having the 2-methylallyl substituent exo to the metal. The co-ordination of the η5-1,2,3,3a-tetrahydropentalenyl ligand is slightly asymmetric with the substituted cárbons furthest from the cobalt. The observed structure shows that complexes (3) may also be regarded as substituted cobaltocenium salts, and as such undergo reversible one-electron reduction to the corresponding cobaltocenes at a platinum bead electrode in CH2Cl2.

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Article information


J. Chem. Soc., Dalton Trans., 1988, 1631-1636
Article type
Paper

Allylation of cobalt-co-ordinated cyclo-octatetraene by the [Fe{P(OMe)3}(NO)23-allyl)]+ cation: ring closure to 1,2,3,3a-tetrahydropentalenyl derivatives and the X-ray structure of [Co(η5-C8H8R)(η-C5Me5)][PF6][R = CH2C(Me)[double bond, length half m-dash]CH2]

N. G. Connelly, M. Gilbert, A. G. Orpen and J. M. White, J. Chem. Soc., Dalton Trans., 1988, 1631
DOI: 10.1039/DT9880001631

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