Heavier pnictinidene gold(i) complexesElectronic supplementary information (ESI) available: Details of crystallographic and theoretical studies. CCDC 1553193-1553198 and 1555817. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt03022g

• Main Authors: Ko enková, Monika, Kremlá ek, Vít, Erben, Milan, Jirásko, Robert, De Proft, Frank, Turek, Jan, Jambor, Roman, R i ka, Aleš, Císa ová, Ivana, Dostál, Libor
• Format: Journal Article
• Published: 23.10.2018
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c8dt03022g

N , C , N -Chelated pnictinidenes ArE [where E = As, Sb or Bi; Ar = 2,6-( t BuN&z.dbd;CH) 2 C 6 H 3 ] were used as ligands for the coordination of various gold( i ) complexes. Thus, the reaction of ArE with [AuCl(Me 2 S)] 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 2 S)] 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(C&z.tbd;CPh)] 4 with ArAs and ArSb gave ionic compounds [Au(ArAs) 2 ] + [Au 2 (C&z.tbd;CPh) 3 ] − [denoted as 3 + [Au 2 (C&z.tbd;CPh) 3 ] − ] and [Au(ArSb) 2 ] + [Au(C&z.tbd;CPh) 2 ] − [denoted as 4 + [Au(C&z.tbd;CPh) 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 1 H and 13 C 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. Novel pnictogen( i ) → Au( i ) complexes were isolated including a unique example of the bismuthinidene complex containing the first Bi( i ) → Au( i ) bond.