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

Abstract

Treatment of Au(PPh 3)Cl, (AuCl) 2( trans-dpen) and (AuCl) 2(dppfe) with Sn(SPh)( n-Bu) 3 and/or PhSH/KOH affords Au(PPh 3)(SPh) ( 1), (AuSPh) 2( μ- trans-dpen) ( 2), (AuSPh)2( μ-dppfe) ( 3), (AuSPh)( μ- trans-dpen)(AuCl) ( 4), and (AuSPh)( μ-dppfe)(AuCl) ( 5) in good yields. All these thiophenolates are characterized by single crystal X-ray analysis, 1H and 31P NMR spectroscopy. 1 forms tetramer through Au⋯Au interaction and π–π interaction between the phenyl group in SPh and one of the phenyl groups in PPh 3 in the solid state. An infinite chain structure is formed for 2 through intermolecular aurophilicity and these chains are connected by partial overlap (π–π interaction) of neighboring phenyl groups in SPh to give two-dimensional networks in the solid state. Similar infinite chains are formed through aurophilicity, but two-dimensional networks are not formed for 4 in the solid state. No multidimensional structure is formed for 3 and 5 in the solid state. 1H and 31P NMR spectroscopy of CDC1 3 solutions of 2, 3, 4, and 5 has revealed that rapid ligand scrambling takes place for 4 and 5.