Preparation, structure, and reactions of some new complexes containing copper or silver bonded to various transition metals

Abstract

The complexes [Me₄N][Ag{M(CO)₃(cp)}₂], [Me₄N][Cu{M(CO)₃(cp)}₂],[{(cp)M(CO)₃Ag}_n],[{(cp)M(CO)₃Cu(L)_x}_n][M = Cr, Mo, or W; (L)_x= OH₂ or ½OH₂·½NH₃; cp =η-cyclopentadienyl][{Co(CO)₄Ag}_n][{Co(CO)₄Cu(L)_y}_n][{(Bu₃P)Co(CO)₃Ag}_n][{(Bu₃P)Co(CO)₃Cu}_n], [{[(PhO)₃P]Fe(CO)₂(NO)Ag}_n], [{HFe(CO)₄Ag}₂]·-AgNO₃, and [V(CO)₆Cu(L–L₎2](L–L = 1,10-phenanthroline or 2,2′-bipyridyl) are described, many for the first time, and their i.r. spectra reported. It is suggested that the neutral complexes are covalent oligomers with n=ca. 3 or 4 which tend to ionize in donor solvents. All the complexes form 1 : 1 adducts with L–L; many of these are ionic. Scission reactions with Ph₃SnCl, Ph₃PbCl, l₂, Mel, or mercury are described for the derivatives of Cr, Mo, or W. The salt Na(C₅H₅) converts [{(cp)Mo(CO)₃Ag}_n] to [Ag{Mo(CO)₃(cp)}₂]⁺; Et₂O·BF₃ reverses the reaction.