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Keywords:

  • Phosphorus-nitrogen heterocycles;
  • Diphosphanes;
  • X-ray diffraction;
  • Substituent effects;
  • Structure correlation

Abstract

2-Diphenylphosphanyl-1,3,2-diazaphospholidines were prepared via metathesis from 2-chloro-1,3,2-diazaphospholidines and LiPPh2. For some of the products, symmetrisation to tetraphenyldiphosphane and 2,2′-bis-1,3,2-diazaphospholidinyls was observed. Most of the derivatives were characterised by single-crystal X-ray diffraction, which showed that all compounds studied feature elongated exocyclic P–Cl or P–P-bonds, respectively. The extent of this bond lengthening is in the P-phosphanyl-substituted species similar and in the P-chloro-derivatives less pronounced than in corresponding CC-unsaturated 1,3,2-diazaphospholenes. Structure correlation involving comparison of exocyclic P–X and endocyclic P–N distances suggests that n(N)/σ*(P–X) hyperconjugation contributes strongly to the bond lengthening and induces a perceptible weakening of the P–P bonds in 2-diphenylphosphanyl-1,3,2-diazaphospholidines, which should render these compounds interesting substrates for P–P bond activation reactions.