Binuclear Macrocyclic Silver(I) Complex of a Bis(carbone) Pincer Ligand: Synthesis and Application as a Carbone-Transfer Agent.

A facile synthesis of a binuclear Ag complex of a bis(carbone) ligand and its application as a carbone-transfer agent for the generation of other transition-metal complexes of Au (), Ni (), and Pd () is presented. Complex was synthesized through multiple synthetic routes under mild reaction conditions using the tetracationic [H][OTf·Cl] precursor salt, the dicationic [H][OTf] ylide salt, and the free ligand . The first two synthesis routes require no prior isolation of the air-, moisture-, and temperature-sensitive free ligand , thus affording complex with high yield and purity. Multinuclear NMR techniques, high-resolution mass spectrometry, and single-crystal X-ray diffraction analysis confirmed the identity of complex as a binuclear Ag complex of with a molecular formula of [Ag][OTf] and a 16-membered-ring metallomacrocyclic structure. During the transmetalation reaction with Au, the binuclear nature of complex remains intact to give analogous complex ([Au][OTf]). However, the dimeric structure was disrupted upon the carbone-transfer reaction with Ni and Pd, yielding mononuclear C-N-C pincer-type complexes ([NiCl][OTf]) and ([PdCl][OTf]), respectively. These results demonstrated the versatile use of complex as a carbone-transfer agent to other transition metals regardless of the type or size of the metals or the geometry they prefer.