The bimetallic activation of white phosphorus by trans-[RhCl(CO)(dppm)] 2 results in a Tetrahedro-Rh2P2 Moiety

Maria Caporali, Luca Gonsalvi, Vincenzo Mirabello, Andrea Ienco, Gabriele Manca, Fabrizio Zanobini, Maurizio Peruzzini

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

The 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-κ22-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 P 2 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. The new complex cis-[Rh2(CO)2(μ-dppm) 2(μ,η2-P2)], obtained by activation of white phosphorus under mild conditions, was fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The P2 unit acts as an eight-electron donor with all the π* combinations occupied and donates into four empty metal combinations, as described by theoretical analysis. Copyright

Original languageEnglish
Pages (from-to)1652-1659
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2014
Issue number10
DOIs
Publication statusPublished - 1 Apr 2014

Keywords

  • Metal-metal interactions
  • Phosphine ligands
  • Phosphorus
  • Rhodium

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