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Updated: Apr 6, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Synthesis and structures of [S=(H)P(μ-NR)]2, potential building blocks for inorganic phosphorus-sulfur macrocycles
Callum G M Benson1, Vladislav Vasilenko, Raúl García-Rodríguez
1Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB2 1EW, UK. dsw1000@cam.ac.uk.
Abstract:
The reactions of the chloro-phosph(iii)azane dimers [ClP(μ-NR)]2 with LiSH give the dimers [S[double bond, length as m-dash](H)P(μ-NR)]2 (), which are potential new building blocks for inorganic macrocycles of the type [{P(μ-NR)}2(μ-S)]n. NMR spectroscopic studies and DFT calculations show that the preference for the cis or trans isomers of is largely influenced by the steric demands of the R-group, with cis isomers being preferred for bulky substituents. This is an important factor in regard to applications in macrocycle synthesis since the cis arrangement is pre-organized for cyclisation.
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