Synthesis, X-ray molecular structure analysis, and study on ligand scrambling reactions of new thiolatogold(I) complexes with various phosphines

Treatment of Au(PPh3)Cl, (AuCl)(2)(trans-dpen) and (AuCl)(2)(dppfe) with Sn (SPh)(n-Bu)(3) and/or PhSH/KOH affords Au(PPh3)(SPh) (1), (AuSPh)(2)(mu -tr ans-dpen) (2), (AuSPh)2(mu -dppfe) (3), (AuSPh)(mu -trans-dpen)(AuCl) (4), and (AuSPh)-(mu -dppfe)(AuCl) (5) in good yields. All these thiophenolates are characterized by single crystal X-ray analysis, H-1 and P-31 NMR spectr oscopy. 1 forms tetramer through Au . . . Au interaction and pi-pi interact ion between the phenyl group in SPh and one of the phenyl groups in PPh3 in the solid state. An infinite chain structure is formed for 2 through inter molecular aurophilicity and these chains are connected by partial overlap ( pi-pi interaction) of neighboring phenyl groups in SPh to give two-dimensio nal networks in the solid state. Similar infinite chains are formed through aurophilicity, but two-dimensional networks are not formed for 4 in the so lid state. No multidimensional structure is formed for 3 and 5 in the solid state. H-1 and P-31 NMR spectroscopy of CDCl3 solutions of 2, 3, 4, and 5 has revealed that rapid ligand scrambling takes place for 4 and 5. (C) 2001 Elsevier Science B.V. All rights reserved.