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A Modular Approach to Inorganic Phosphazane Macrocycles
Author(s) -
Plajer Alex J.,
GarcíaRodríguez Raúl,
Benson Callum G. M.,
Matthews Peter D.,
Bond Andrew D.,
Singh Sanjay,
Gade Lutz H.,
Wright Dominic S.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702558
Subject(s) - supramolecular chemistry , chemistry , electrophile , molecule , modular design , combinatorial chemistry , bridging (networking) , nanotechnology , stereochemistry , materials science , organic chemistry , catalysis , computer science , computer network , operating system
Abstract Inorganic macrocycles, based on non‐carbon backbones, present exciting synthetic challenges in the systematic assembly of inorganic molecules, as well as new avenues in host–guest and supramolecular chemistry. Here we demonstrate a new high‐yielding modular approach to a broad range of trimeric and hexameric S‐ and Se‐bridged inorganic macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H)P(μ‐NR)] 2 . The method involves the in situ generation of the key intermediate [E. . . . . _ (S. . . . . _ )P(μ‐NR)] 2 2− (E=S, Se) dianion, which can be reacted with electrophilic [ClP(μ‐NR)] 2 to give P III /P V hexameric rings or reacted with I 2 to give trimeric P V variants. Important issues which are highlighted in this work are the competitive bridging ability of S versus Se in these systems and the synthesis of the first air‐stable and chiral inorganic macrocycles.