The Bimetallic Activation of White Phosphorus by trans‐[RhCl(CO)(dppm)]2 Results in a Tetrahedro‐Rh2P2 Moiety

Abstract

AbstractThe reaction of trans‐[RhCl(CO)(dppm)]2 with P4 carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P4, giving a μ,η2‐P2 (μ‐κ2:κ2‐P2) ligand coordinated to the two metal centres. The new complex cis‐[Rh2(CO)2(μ‐dppm)2(μ,η2‐P2)] has been fully characterised in solution by NMR spectroscopy and in the solid state by single‐crystal X‐ray diffraction. The Rh–Rh distance of 2.723(18) Å is consistent with the presence of a metal–metal single bond, which was supported by theoretical analysis showing that the HOMO of the complex has metal–metal bond character. A literature survey revealed that, in most cases, the P2 unit acts as a P24– ligand, and also in the case at hand the diphosphenyl ligand behaves as an eight‐electron donor with all the π* combinations occupied and donates into four empty metal combinations.