화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.131, No.31, 11249-11255, 2009
Monomeric Copper(I), Silver(I), and Gold(I) Alkyne Complexes and the Coinage Metal Family Group Trends
A series of thermally stable, easily isolable, monomeric, and isoleptic coinage metal alkyne complexes have been reported. Treatment of [N{(C3F7)C(Dipp)N}(2)]Li (the lithium salt of the 1,3,5-triazapentadiene [N{(C3F7)C(Dipp)N}(2)]H) with AuCl, CF3SO3Ag or CF3SO3CU in the presence of 3-hexyne led to the corresponding coinage metal alkyne complex [N{(C3F7)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 eta(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{(CF3)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 a-donation from alkyne -> M dominates over the M -> alkyne pi-back-donation.