Structure-Analytical Investigations of P-Substituted 1,3,2-Diazaphospholidines

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)/sigma*(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.