Volume 58, Issue 31 pp. 10655-10659
Communication

Guest Binding via N−H⋅⋅⋅π Bonding and Kinetic Entrapment by an Inorganic Macrocycle

Alex J. Plajer

Alex J. Plajer

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK

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Dr. Felix J. Rizzuto

Dr. Felix J. Rizzuto

Department of Chemistry, McGill University, 801 Sherbrooke St. W, Montreal, Quebec, H3A 0B8 Canada

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Hao-Che Niu

Hao-Che Niu

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK

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Sanha Lee

Sanha Lee

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK

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Prof. Jonathan M. Goodman

Prof. Jonathan M. Goodman

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK

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Prof. Dr. Dominic S. Wright

Corresponding Author

Prof. Dr. Dominic S. Wright

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW UK

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First published: 03 June 2019
Citations: 14

Graphical Abstract

Ringing the Changes: The inorganic phosph(III)azane [{P(μ-NtBu)}2NH]5 macrocycle provides a unique H-bonding host environment for N−H⋅⋅⋅π bonding to alkynes, nitriles, and the PCO anion. Oxidation of the PIII periphery with sulfur kinetically entraps halide ion guests, which cannot be abstracted even with powerful methylating agents.

Abstract

Modern supramolecular chemistry is overwhelmingly based on non-covalent interactions involving organic architectures. However, the question of what happens when you depart from this area to the supramolecular chemistry of structures based on non-carbon frameworks remains largely unanswered, and is an area that potentially provides new directions in molecular activation, host–guest chemistry, and biomimetic chemistry. In this work, we explore the unusual host–guest chemistry of the pentameric macrocycle [{P(μ-NtBu}2NH]5 with a range of anionic and neutral guests. The polar coordination site of this host promotes new modes of guest encapsulation via hydrogen bonding with the π systems of the unsaturated C≡C and C≡N bonds of acetylenes and nitriles as well as with the PCO anion. Halide guests can be kinetically locked within the structure by oxidation of the phosphorus periphery by oxidation to PV. Our study underscores the future promise of p-block macrocyclic chemistry.

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