Chemistry of the cyclopentadienylmetal carbonyls. VII. Nucleophilic substitution reactions of cyclopentadienyliron, -tungsten, and -molybdenum carbonyl cations

Article abstract of DOI:10.1021/ic50053a013

Reactions of pentafluorophenyllithium and phenyllithium with the cationic species C₅H₅Fe(CO)₃⁺, C₅H₅Fe(CO)₂[(C₆H₅) ₃P]⁺, C₅H₅Fe(CO)₂py⁺, C₅H₅Fe(CO)₂(CH₃CN)⁺, C₅H₅M(CO)₄⁺, and C₅H₅M(CO)₃L⁺(M = Mo, W; L = (C₆H₅)₃P, (C₆H₅)₃As) have been studied. Depending on the nature of the metal and the ligands substituted on the metal, the reaction that occurs is: (a) reaction at a carbonyl to give an acyl metal derivative, (b) displacement of a ligand to give an aryl metal compound, (c) reaction at the cyclopentadienyl ring to give a 1-arylcyclopentadiene complex, and/or (d) reduction to give the corresponding biaryl and a dimeric cyclopentadienylmetal carbonyl. The reaction of NaBH₄ and C₅H₅M(CO)₄⁺ gives C₅H₅M(CO)₃H (M = Mo, W), in a reaction analogous to (b) above. The reaction of KaBH₄ and C₅H₅M(CO)₃[(C₆H₅) ₃P]⁺ surprisingly gives C₅H₅M(CO)₂[(C₆H₅) ₃P]CH₃ (M = Mo, W) in high yield. A possible mechanism for this reaction is suggested.