Solvent-free substitution reactions of solid phosphines with (η5-RC5H4)Fe(CO)2i (R = H, Me) complexes

Article abstract of DOI:10.1515/znb-2007-0320

Reactions of (η⁵-RC₅H₄)Fe(CO) ₂I (R = H, Me) complexes with phosphine ligands PR′ ₃3 (R′ = Ph, m-Tol, p-C₆H₄OMe, p-C ₆H₄Cl, p-C₆H₄F) have been performed under solvent-free conditions in the melt phase and generally yielded the ionic products [(η⁵5-RC₅H₄)Fe(CO) ₂PR′₃]I rather than the CO substituted products (η⁵-RC₅H₄)Fe(CO)(PR′₃)I. The complexes have been characterised by IR, NMR and MS techniques. By contrast, the same reactions studied in benzene solution have yielded mainly the CO substitution products. Factors that affect the solvent-free reaction include variation in R and R′, reaction temperature and the addition of [CpFe(CO)₂]₂ as a catalyst. The mechanism of the reaction for the formation of the ionic complex is proposed to go via a 19 electron intermediate. This is in contrast to the reaction in bezene that occurs via a 17 electron intermediate, clearly indicating the role of the melt phase in the reaction.

Full text of DOI:10.1515/znb-2007-0320

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