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A Modular Approach to Inorganic Phosphazane Macrocycles

Accepted version
Peer-reviewed

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Type

Article

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Authors

Plajer, Alex J 
García-Rodríguez, Raúl 
Benson, Callum GM 
Matthews, Peter D 
Bond, Andrew D 

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)]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.

Description

Keywords

X-ray structural analysis, macrocycles, modular synthesis, phosphazanes

Journal Title

Angewandte Chemie (International ed. in English)

Conference Name

Journal ISSN

1433-7851
1521-3773

Volume Title

56

Publisher

Wiley
Sponsorship
Engineering and Physical Sciences Research Council (EP/K039520/1)
European Research Council (291280)
European Commission (329283)
We thank the EU (ERC‐advanced grant for D.S.W., studentship for C.G.M.B., Intra European Fellowship Framework 7 for R.G.‐R.), the EPSRC (studentship for P.D.M.) for support, and the University of Heidelberg for travel grants.