An unexpected product isolated during the decomposition of an isomer of Re2Cl2(μ-dppm)2(CO)(CNXyl)3 — synthesis and structural characterization of [Na(dppmO2)3]Cl·2H2O·C6H6

The sodium complex [Na(dppmO2)3]Cl·2H2O·C6H6 (dppmO2=Ph2P(O)CH2P(O)Ph2), which was initially isolated as a minor by-product during studies of the decomposition of Re2Cl2(μ-dppm)2(CO)(CNXyl)3, was prepared by a more logical route involving the reaction of a mixture of dppm and NaCl with 30% H2O2 in aqueous actone followed by recrystallization from ethanol–benzene. A crystal structure determination shows that the coordination geometry around Na is rigorously trigonal prismatic.