Bis(diphenylphosphino)methanedicopper(I) units bridged by dicarboxylates

Two novel compounds, [(μ-dppm)2Cu2(O2CC6H4CO2)Cu2(μ-dppm)2](PF6)2·3.4CH2Cl2 (1·3.4CH2Cl2) and [(μ-dppm)2Cu2(O2CC2F4CO2)Cu2(μ-dppm)2](PF6)2·5CH2Cl2 (2·5CH2Cl2), have been prepared from the reactions of [(μ-dppm)2Cu2(CH3CN)2](PF6)2 with the corresponding dicarboxylate salts, and their structures have been determined crystallographically. The crystal structures of 1 and 2 consist of the complex cations [(μ-dppm)2Cu2(LL)Cu2(μ-dppm)2]2+, in which two dppm-bridged dinuclear copper(I) units are linked by dicarboxylate bridges LL2− (LL=O2CC6H4CO2 and O2CC2F4CO2) in an end-to-end fashion, PF6 − ions and dichloromethane molecules. The Cu⋯Cu separations within the [(μ-dppm)2Cu2]2+ units are 2.707(1) and 2.833(1) Å in 1 and 2, respectively. In both complexes, the copper(I) centers are in a trigonal coordination environment comprised by one O and two P atoms; additional contacts between the Cu centers and chlorine atoms of dichloromethane are observed in 2.