Abstrakt
N,C,N-Chelated pnictinidenes ArE [where E = As, Sb or Bi; Ar = 2,6-(tBuN=CH)(2)C6H3] were used as ligands for the coordination of various gold(I) complexes. Thus, the reaction of ArE with [AuCl(Me2S)] gave complexes [AuCl(ArE)] [where E = As (1) or Sb (2)] that exhibited only limited stability in solution.
By contrast, the reaction of ArBi with [AuCl(Me2S)] led to the immediate deposition of gold metal and the oxidation of the bismuth atom giving ArBiCl2. The treatment of a tetrameric gold alkynyl complex [Au(CuCPh)](4) with ArAs and ArSb gave ionic compounds [Au(ArAs)(2)](+)[Au-2(C=CPh)(3)](-) [denoted as 3(+)[Au-2(C=CPh)(3)](-)] and [Au(ArSb)(2)](+)[Au(CuCPh)(2)](-) [denoted as 4(+)[Au(CuCPh)(2)](-)], respectively.
Finally, the reaction of ArE with the carbene gold(I) complex [Au(IPr)(MeCN)](+)[BF4](-)[where IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, MeCN = acetonitrile] produced ionic complexes [Au(IPr)(ArE)]+[BF4][ for cations: E = As (5(+)), Sb (6(+)) or Bi (7(+))]. All complexes were characterized using H-1 and C-13 NMR, high mass accuracy electrospray ionization mass spectrometry (ESI-MS), IR and Raman spectroscopy and (except for 1) by single-crystal X-ray diffraction analysis.
Furthermore, the structure and bonding of both neutral and ionic complexes with different coordination patterns have also been investigated in detail using a Density Functional Theory (DFT) computational approach.