Abstract

MUNYANEZA, Apollinaire; BALA, Muhammad D.  and  COVILLE, Neil J.. Solventless substitution reaction of solid phosphine ligands with Ru(C₅H₄R)(CO)₂I (R = H, Me). S.Afr.j.chem. (Online) [online]. 2009, vol.62, pp.14-19. ISSN 1996-840X.

The solventless reaction between Ru(C₅H₄R)(CO)₂I (R = H, Me) and solid phosphine ligands [PPh_3/ P(p-MeOC₆H₄)₃, P(m-MeC₆H₄)₃,P(p-FC₆H₄)₃,P(p-ClC₆H₄)₃] was undertaken at various temperatures with all the reactions occurring in the melt phase. The reaction rates and type of products isolated are dependent on the electronic properties of the Cp-substituent and the para-substituent on the phosphine ligands. For the C₅H₄R moiety, when R = H the ligand substitution product Ru(C₅H₅)(CO)(PR₃) I was obtained, and the ligand addition product [Ru(C₅H₄Me)(CO)₂(PR₃)]I was predominantly obtained when R = Me. The reaction rates are enhanced by para-substituted electron-donating phosphines. These results are similar to those obtained from studies utilizing benzene and xylene as solvents. The products have been characterized by FTIR and NMR spectroscopy and by MS. The complex Fe₂(C₅H₅)₂(CO)₄ was found to act as a catalyst in all the melt reactions.

Keywords : Solvent-free; ruthenium; cyclopentadienyl complexes; phosphines.

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