1,3-Dipolar cycloaddition between a metal-azide (Ph_3PAuN _3) and a metal-acetylide (Ph_3PAuCCPh): An inorganic version of a click reaction

摘要

This report describes the synthesis and characterization of 1,5-bis-triphenylphosphinegold(i) 1,2,3-triazolate (3_((1,5))). The synthesis of the dinuclear complex 3_((1,5)) is achieved via an unprecedented inorganic click (iClick) reaction between the metal-azide PPh _3AuN_3 (1) and the metal-acetylide PPh_3Au-CCPh (2). Characterization of 3_((1,5)) includes multinuclear NMR spectroscopy, combustion analysis, and single crystal X-ray crystallography. Experimental characterization is complemented with density-functional-theory (DFT) calculations which indicate the 1,4-isomer 3_((1,4)) is less stable by 3.3 kcal mol~(-1). The energetic difference lies primarily in the ability of the phenyl group in the 4-position of 3_((1,5)) to lie coplanar with the triazolate to create a delocalized π-bonding HOMO orbital.