Phosphane Chalcogenides and their Metal Complexes. II. Gold(I) Halide Complexes of some Diphosphane Monochalcogenides

We report the crystal structures of 19 gold(I) complexes with diphosphane monochalcogenide ligands, general formula (PP)EAuHal (PP = diphosphane, E = chalcogen, Hal = halogen). For PP = bis(diphenylphosphano)methane (dppm): 1, dppmOAuCl as its diisopropyl ether solvate; 2, dppmOAuI as its dichloromethane solvate; 3, dppmSAuCl as its dichloromethane hemisolvate; 4, dppmSAuI; 5, dppmSeAuBr as a 1:1 adduct with dppmSe₂; 6, dppmSeAuI. Compound 3 is isotypic to the known structure of dppmSeAuCl. Most of the structures have an E–P···P–Au torsion angle close to zero, which, especially for the larger E atoms, facilitates a close intramolecular approach of E and Au. The packing of 1–3 involves hydrogen bonds from the methylene hydrogens. For PP = 1,2-bis(diphenylphosphano)ethane (dppe): 7, dppeOAuBr and 8, dppeOAuI, both as their hemihydrates; 9, dppeSAuBr; 10, dppeSAuI. All four compounds crystallise with two independent molecules of the gold complex, between which short Au···Au contacts are observed; the molecules of 7 and 8 are further linked by hydrogen bond systems […P=O···H–O–H···O=P…]. Compounds 7 and 8 form an isotypic series with their known chloride analogue, as do 9 and 10. For PP = 1,2-bis(diphenylphosphano)benzene (dppbz): 11, dppbzOAuCl; 12, dppbzOAuBr; 13, dppbzSAuBr; 14, dppbzSAuI, 16, dppbzSeAuBr and 17, dppbzSeAuI, all as their isotypic dichloromethane disolvates; 15, dppbzSeAuCl (isotypic to 13). The absolute E–P···P–Au torsion angles are all in the range 50–70^○; short intramolecular E···Au contacts are observed. The packing of 11–17 shows few notable short contacts. For PP = cis-1,2-bis(diphenylphosphano)ethene (^cisdppen): 18, ^cisdppenSAuCl; 19, ^cisdppenSAuBr. Both compounds crystallise with two independent molecules, and in both cases the molecules display considerable differences in configuration. The packing of 18 involves short H···Cl and that of 19 short H···S contacts. For PP = 1,8-bis(diphenylphosphano)naphthalene (dppn), an inversion-symmetric gold(III) complex (dppnSeAu)₂Cl₂ 20, with a central four-membered ring Au₂Se₂, was obtained instead of the expected isomeric gold(I) derivative by formal insertion of gold into a P–Se bond; it crystallised as a deuterochloroform hexasolvate.