Incorporation of an N-heterocyclic phosphenium (NHP) cation into a diphosphine pincer ligand framework has allowed for a systematic investigation of the coordination chemistry of these ligands.  Coordination of the NHP-diphosphine to Pd0 or Pt0 leads to two-electron oxidation of the metal center and reduction of the phosphenium unit to generate a metal-phosphido species, as indicated by the pyramidal geometry of the NHP unit.  Interestingly, the geometry of the NHP unit can be interconverted by two-electron redox changes or by binding/dissociation of two electron donors ligands, rendering NHPs sterically and electronically tunable analogues of nitrosyls.  Further exploration of the coordination chemistry of these NHP-diphosphine ligands and the resulting redox properties of their metal complexes will be discussed.

Incorporation of N-heterocylic phosphenium (NHP) cations into a pincer ligand framework: NHPs as sterically and electronically tunable nitrosyl analogs

245th National Meeting (2013)

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