Heterobimetallic Coinage Metal‐Ruthenium Complexes Supported by Anionic N‐Heterocyclic Carbenes

The lithium complexes [(WCA‐NHC)Li(toluene)] of anionic N‐heterocyclic carbenes with a weakly coordinating borate moiety (WCA‐NHC, WCA=B(C(6)F(5))(3), NHC=IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were used for the preparation of silver(I) or copper(I) WCA‐NHC complexes. While the reactions in THF with AgCl or CuCl afforded anionic mono‐ and dicarbene complexes with solvated lithium counterions [Li(THF)(n)](+) (n=3, 4), the reactions in toluene proceeded with elimination of LiCl and formation of the neutral phosphine and arene complexes [(WCA‐NHC)M(PPh(3))] and [(WCA‐NHC)M(η (2)‐toluene)] (M=Ag, Cu). The latter were used for the preparation of chlorido‐ and iodido‐bridged heterobimetallic Ag/Ru and Cu/Ru complexes [(WCA‐NHC)M(μ‐X)(2)Ru(PPh(3))(η (6)‐p‐cymene)] (M=Ag, Cu, X=Cl; M=Ag, X=I). Surprisingly, these complexes resisted the elimination of CuCl, AgCl, or AgI, precluding WCA‐NHC transmetalation.