Copper(I) Chloride Cluster Complexes with Pentaphenyl‐Cyclopentaphosphane as Ligand

Pentaphenylcyclopentaphosphane, c ‐(P 5 Ph 5 ) is conviently prepared from PhPCl 2 and thermally activated zinc powder in thf. Hydrolysis of c ‐(P 5 Ph 5 ) in the presence of ZnCl 2 gives to an equimolar distribution of PhPH 2 , PhP(=O)H 2 , and PhP(=O)(OH)H. Reaction of c ‐(P 5 Ph 5 ) with Cu I Cl leads to the tetranuclear copper(I) chloride complex [Cu 4 (μ 4 ‐Cl) 2 (μ 2 ‐Cl) 2 { c ‐(P 5 Ph 5 )} 2 ] with a Cu 4 (μ 4 ‐Cl) 2 (μ 2 ‐Cl) 2 cluster core and the hexanuclear [Cu 6 (μ 3 ‐Cl) 2 (μ 2 ‐Cl) 2 { c ‐(P 5 Ph 5 )} 2 (thf) 2 ]. Hydrolysis of the copper c ‐(P 5 Ph 5 ) complexes leads to significantly higher amounts of the primary phosphane oxide PhP(=O)H 2 .