PNNL

Abstract

There have been intense recent interests in the homogeneous catalytic chemistry of Au(I) complexes.1 Among the Au(I) molecules, the Au(CN)2- ion is the most stable and has been widely used in gold extraction back to ancient times. Although AuCN in the condensed phase has been studied, including solution phase vibrational spectroscopy2 and crystal structures,3 the free AuCN molecule has been studied only very recently by microwave spectroscopy.4 The important Au(CN)2- complex has not been observed and studied in the gas phase. Because of the relativistic effects,5 Au-containing molecules exhibit distinctly different properties among the coinage elements. To elucidate the nature of the Au-ligand binding, high-level ab initio calculations are needed due to the complicated electron correlation and relativistic effects.6-8 The structure and bonding of the AuCN molecule were first examined computationally by Frenking and co-workers.7 Recent high-precision calculations by Pyykkö and co-workers suggest multiple-bond characters between Au-C in AuCN because the Au-C bond length is only slightly longer than the sum of the triple bond covalent radii.