4 years ago

A Modular Approach to Inorganic Phosphazane Macrocycles

A Modular Approach to Inorganic Phosphazane Macrocycles
Andrew D. Bond, Callum G. M. Benson, Peter D. Matthews, Alex J. Plajer, Lutz H. Gade, Sanjay Singh, Dominic S. Wright, Raúl García-Rodríguez
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)]22−(E=S, Se) dianion, which can be reacted with electrophilic [ClP(μ-NR)]2 to give PIII/PV hexameric rings or reacted with I2 to give trimeric PV 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. Give me a ring: A range of new S- or Se-bridged phosphazane macrocycles can be obtained using the dimeric dianions [S=(Se)P(μ-NtBu)]22−, either through reactions with the dichlorophosphazane dimers [ClP(μ-NR)]2 or by oxidation with I2. This approach allows variation of the organic substituents in this class of inorganic macromolecule for the first time, and the introduction of chirality.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702558

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