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{(C(3)F(7))C(Dipp)N}(2)]Li (the lithium salt of the 1,3,5-triazapentadiene [N{(C(3)F(7))C(Dipp)N}(2)]H) with AuCl, CF(3)SO(3)Ag or CF(3)SO(3)Cu in the presence of 3-hexyne led to the corresponding coinage metal alkyne complex [N{(C(3)F(7))C(Dipp)N}(2)]M(EtC[triple bond]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[triple bond]C bond angle is largest for the gold, followed by Cu and Ag adducts. The gold adduct also shows the largest decrease in C[triple bond]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[triple bond]CEt) and the related ClM(EtC[triple bond]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[triple bond]C, largest deviation of C-C[triple bond]C bond angle from linearity, and smallest C[triple bond]C stretching frequency, followed by the Cu and Ag adducts. In these triazapentadienyl coinage metal adducts, the sigma-donation from alkyne --> M dominates over the M --> alkyne pi-back-donation.
Dias
H V Rasika
HV
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019, USA. dias@uta.edu
Flores
Jaime A
JA
Wu
Jiang
J
Kroll
Peter
P