X-ray crystallographic and extended X-ray absorption fine structure studies of gold(I) complexes containing weak intermolecular interactions

摘要

The crystal and molecular structures of [Au-2{S2CN(C2H4OMe)(2)}(2)], [Au(PPh3)(SCH2CO2H)], [Au(PPh3)(SCMe2CO2H)] and [Au(PPh3)(SCH2CO2Me)] have been determined. All compounds contain an approximately linear primary co-ordination sphere of ligands about the gold atom, but they differ markedly in their type of intermolecular interaction. In [Au-2{S,CN(C2H4OMe)(2)}(2)] the supramolecular array is dominated by an almost linear, polymeric backbone of gold atoms with alternate gold-gold contacts of 2.7902(6) (intramolecular) and 3.1572(7) Angstrom (intermolecular), whereas in [Au(PPh3)(SCH2CO2H)] dimers associated through long gold-sulfur contacts of 3.131(2) Angstrom are held together in a polymeric chain by hydrogen bonding between neighbouring carboxylic acid residues. The increased steric bulk of the thiolate ligand in [Au(PPh3)(SCMe2CO2H)] caused by the methyl groups on the alpha-carbon atom precludes association of the gold centres, but hydrogen bonding between carboxylates as in the SCH2CO2H compound causes dimerisation. Compound [Au(PPh3)(SCH2CO2Me)] exists as a monomer with no evidence of weak intermolecular interactions. Analysis of ambient-temperature EXAFS (extended X-ray absorption fine structure) measurements on solid samples of the first two compounds yield gold-gold separations of 2.775(2) and 3.271(6) Angstrom and 4.188(15) Angstrom, respectively. Gold-sulfur separations of 2.290(1) and 3.532(8) and of 2.329(4) and 3.124(19) Angstrom, respectively, are also in good agreement with X-ray data. [References: 47]