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

The reaction between thioether phosphine gold(I) precursors such as [AuCl(Ph2PCH2SPh)], 1, or [Au(Ph2PCH2-SPh)(2)]CF3SO3 and PdCl2(NCPh)(2) affords the new compounds [{AuCl(Ph2PCH2SPh)}(2)PdCl2], 2, and [AuPdCl2(Ph-2-PCH2SPh)(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 Moller-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.