Reactions of transition-metal vapours with cycloheptatriene and cyclo-octatetraene

Abstract
The co-ordination of cycloheptatriene in reactions with transition-metal atoms in the condensed phase at low temperature is accompanied by extensive hydrogen migration. Thus, condensation of C7H8 with the vapours of Ti, V, Cr, Fe, and Co affords [Ti(η-C7H7)(η5-C7H9)], V(C14H16), [Cr(η-C7H7)(η4-C7H10)], [Fe(η5-C7H7)(η5-C7H9)] or FeC14H18, and CoC14Hn(n= 15, 17, or 19) respectively. No organometallic products have been isolated from vapours of Mn, Ni or Pd. Condensation of a PF3–C7H8 mixture with vapours of Cr or Co affords [Cr(C7H8)(PF3)3] or [Co(C7H7)(PF3)3] respectively. Condensation of C8H8 with vapours of Ti, Fe, and Co gives intractable polymers, but with chromium vapour [Cr2(C8H8)3] is obtained. The use of metal atoms in the preparation of olefinic metal complexes is compared with conventional reductive methods.

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