Compounds Featuring the Structural Fragment P-C-P

Shevchenko, I. V.; Tarasevich, A. S.; Turcheniuk, Kostiantyn; Mikolenko, Rostislav; Andrushko, Vasyl; Rozhenko, Alexander; Schmutzler, Reinhard; Grützmacher, H.; Roeschenthaler, Gerd‐Volker

doi:10.1080/10426507.2010.520285

Cited by 2 publications

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“…Expectedly, an amine group acting as a Lewis basic counterpart may be successfully replaced by a phosphine moiety. In the literature, there have been only a few reports on the synthesis and reactivity of phosphinophosphoranes, including species with direct P–P − bonds as well as methylene- and sulfur-bridged geminal phosphinophosphoranes. ,, The presented results show that Lewis acidic and Lewis basic centers in ambiphilic P-systems can cooperate in reactions with small organic molecules, such as ketones, isocyanates, and azides, to yield phosphinophosphorylation products (Scheme C). Despite promising preliminary research on geminal phosphinophosphoranes, these systems seem to fade into oblivion, and their chemistry remains unexplored.…”

Section: Introductionmentioning

confidence: 81%

Phosphinophosphoranes: Mixed-Valent Phosphorus Compounds with Ambiphilic Properties

2022

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Herein, we present a simple synthesis of mixed-valent phosphinophosphoranes bearing three-and five-coordinate phosphorus centers. Compounds with phosphorus−phosphorus bonds were synthesized via a reaction of lithium phosphides RR′PLi with cat 2 PCl (cat = catecholate), whereas derivatives with methylene-linked phosphorus centers were obtained via a reaction of phosphanylmethanides RR′CH 2 Li with cat 2 PCl. The presence of accessible lone-pair electrons on the P-phosphanyl atom of phosphinophosphoranes during the reaction of the title compounds with H 3 B•SMe 2 , where phosphinophosphorane-borane adducts were formed quantitatively, was confirmed. Furthermore, the Lewis basic and Lewis acidic properties of the phosphinophosphoranes in reactions with phenyl isothiocyanate were tested. Depending on the structure of the starting phosphinophosphorane, phosphinophosphorylation of PhNCS or formation of a five-membered zwitterionic adduct was observed. The structures of the isolated compounds were unambiguously determined by heteronuclear nuclear magnetic resonance spectroscopy and single-crystal X-ray diffraction. Moreover, by applying density functional theory calculations, we compared the Lewis basicity and nucleophilicity of diversified trivalent P-centers.

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