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Structure‐Analytical Investigations of P‐Substituted 1,3,2‐Diazaphospholidines
Author(s) -
Puntigam Oliver,
Hajdók Imre,
Nieger Martin,
Niemeyer Mark,
Strobel Sabine,
Gudat Dietrich
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100023
Subject(s) - hyperconjugation , double bond , chemistry , metathesis , stereochemistry , crystallography , medicinal chemistry , molecule , polymer chemistry , polymerization , organic chemistry , polymer
2‐Diphenylphosphanyl‐1,3,2‐diazaphospholidines were prepared via metathesis from 2‐chloro‐1,3,2‐diazaphospholidines and LiPPh 2 . 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.