Monomeric Copper(l), Silver(l), and Gold(l) Alkyne Complexes and the Coinage Metal Family Group Trends

摘要

A series of thermally stable, easily isolable, monomeric, and isoleptic coinage metal alkyne complexes have been reported. Treatment of [N{(C_3F_7)C(Dipp)N}_2]Li (the lithium salt of the 1,3,5-triazapentadiene [N{(C_3F_7)C(Dipp)N}_2]H) with AuCI, CF_3SO_3Ag or CF_3SO_3Cu in the presence of 3-hexyne led to the corresponding coinage metal alkyne complex [N{(C_3F_7)C(Dipp)N}_2]M(EtC≡CEt) in good yield (M = Au, Ag, Cu; Dipp = 2,6-diisopropylphenyl). X-ray crystal structures of the three coinage metal alkynes are remarkably similar, and show the presence of trigonal-planar metal sites with η~2-bonded 3-hexyne. The M-C and M-N bond distances vary in the order Cu < Au < Ag. The bending of the C-C≡C bond angle is largest for the gold, followed by Cu and Ag adducts. The gold adduct also shows the largest decrease in C≡C stretching frequency in Raman, while the Ag adduct shows the smallest change compared to that of the uncoordinated alkyne. DFT calculations on [N{(CF_3)C(Ph)N}_2]M(EtC≡CEt) and the related CIM(EtC=CEt) predict that the M-alkyne bond energy varies in the order Ag < Cu < Au. The gold adducts are also predicted to have the longest C≡C, largest deviation of C-C≡C bond angle from linearity, and smallest C≡C stretching frequency, followed by the Cu and Ag adducts. In these triazapentadienyl coinage metal adducts, the cr-donation from alkyne - M dominates over the M → alkyne π-back-donation.