N,C,N-Chelated pnictinidenes ArE [where E = As, Sb or Bi; Ar = 2,6-(tBuNCH) 2C 6H 3] were used as ligands for the coordination of various gold(i) complexes. Thus, the reaction of ArE with [AuCl(Me 2S)] 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(Me 2S)] led to the immediate deposition of gold metal and the oxidation of the bismuth atom giving ArBiCl 2. The treatment of a tetrameric gold alkynyl complex [Au(CCPh)] 4 with ArAs and ArSb gave ionic compounds [Au(ArAs) 2] +[Au 2(CCPh) 3] - [denoted as 3 +[Au 2(CCPh) 3] -] and [Au(ArSb) 2] +[Au(CCPh) 2] - [denoted as 4 +[Au(CCPh) 2] -], respectively. Finally, the reaction of ArE with the carbene gold(i) complex [Au(IPr)(MeCN)] +[BF 4] - [where IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, MeCN = acetonitrile] produced ionic complexes [Au(IPr)(ArE)] +[BF 4] - [for cations: E = As (5 +), Sb (6 +) or Bi (7 +)]. All complexes were characterized using 1H and 13C 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.