A Modular Approach to Inorganic Phosphazane Macrocycles
Benson, Callum GM
Matthews, Peter D
Gade, Lutz H
Angewandte Chemie (International ed. in English)
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Plajer, A., García-Rodríguez, R., Benson, C. G., Matthews, P. D., Bond, A., Singh, S., Gade, L. H., & et al. (2017). A Modular Approach to Inorganic Phosphazane Macrocycles. Angewandte Chemie (International ed. in English), 56 (31), 9087-9090. https://doi.org/10.1002/anie.201702558
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.
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.
European Research Council (291280)
European Commission (329283)
External DOI: https://doi.org/10.1002/anie.201702558
This record's URL: https://www.repository.cam.ac.uk/handle/1810/270093