Silver(I) isocyanide complexes: spectroscopic features and reactions with neutral ligands

Abstract

The silver(I) isocyanide complexes [Ag(CNR)₄]ClO₄(R = Me, cyclo-C₆H₁₁, or Bu^t) and [Ag(CNC₆H₁₁)₂]ClO₄ have been prepared, their i.r., Raman, ¹H and ¹³C n.m.r. spectra recorded, and assignments proposed. Particular emphasis has been placed on an assignment of the vibrational spectrum of [Ag(CNMe)₄]ClO₄. Some reactions of [Ag(CNC₆H₁₁)₂]ClO₄ and [Ag(CNBu^t)₄]ClO₄ with neutral Group 5 donor ligands have been examined. Complete isocyanide displacement leads to the complexes [AgL₄]ClO₄[L = PPh₃, AsPh₃, or P(OMe)₃]. The mixed-ligand complexes [Ag(CNR)(bipy)]ClO₄(R = C₆H₁₁ or Bu^t; bipy = 2,2′-bipyridyl), [Ag(CNC₆H₁₁)₂(py)]ClO₄(py = pyridine), and [Ag(CNC₆H₁₁)L₃]ClO₄[L₃=(Ph₂PCH₂)₃CMe, L = P(OMe)₃] have also been prepared. The complexes involving nitrogen donors appear to contain three-co-ordinate silver(I) whereas those involving phosphorus donors contain four-co-ordinate silver(I).