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