Experimental and Theoretical Studies of the d8−d10 Interaction between Pd(II) and Au(I): Bis(chloro[(phenylthiomethyl)diphenylphosphine]gold(I))−dichloropalladium(II) and Related Systems

Abstract
The reaction between thioether phosphine gold(I) precursors such as [AuCl(Ph2PCH2SPh)], 1, or [Au(Ph2PCH2SPh)2]CF3SO3 and PdCl2(NCPh)2 affords the new compounds [{AuCl(Ph2PCH2SPh)}2PdCl2], 2, and [AuPdCl2(Ph2PCH2SPh)2]CF3SO3, 3. The crystal structure of complex 2 has the sterically unhindered Pd(II) and Au(I) at a distance of 314 pm. Quasirelativistic pseudopotential calculations on [AuPdCl3(PH2CH2SH)(SH2)] models give short Au−Pd distances at the second-order Møller−Plesset (MP2) level and long Au−Pd distances at Hartree−Fock (HF) level. A detailed analysis of the Au−Pd interaction shows dominant dispersion, some ionic contributions, and no net charge transfer between the metals.