Abstract
AbstractReaction of copper halides CuX (X=Cl, Br, I) with tri(2‐pyridylmethyl)amine) (TPMA) in THF under N2 affords a series of monomeric copper(I) complexes CuX(TPMA) (X=Cl (1), Br (2) and I (3)). Treatment of [CuCl(TPMA)] (1) with 0.5 equivalent of 1,4‐diisocyanobenzene following by equimolar amount of NaBF4 affords a novel binuclear complex [(TPMA)Cu(μ‐1,4‐CNC6H4NC)Cu(TPMA)](BF4)2 (4). The copper(I) halide TPMA complexes show interesting fluxional behaviors in temperature dependence in the 1H NMR spectrum that can be explained by the dissociation and reassociation of the pyridyl group and alkylamine nitrogen of TPMA ligand. The crystal structures of 1, 3 and 4 are determined by an X‐ray diffractometer. Complexes 1 and 3 are distorted tetrahedral coordinates with strong bonding between three pyridyl N atoms and the corresponding halide donor. Crystallographic results of 4 clearly indicates two Cu(I) ions are bridged by 1,4‐diisocyanobenzene, forming a centro‐symmetrical homobinuclear complex with a “dangling” uncoordinated pyridyl group.
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