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Spontaneous Decomposition of an Extraordinarily Twisted and Trans-Bent Fully-Phosphanyl-Substituted Digermene to an Unusual Ge^I Cluster

Lookup NU author(s): Dr Keith IzodORCiD, Dr Mo Liu, Dr Peter EvansORCiD, Dr Corinne Wills, Dr Casey Dixon, Dr Paul Waddell, Professor Mike ProbertORCiD

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.Ditetrelenes R2E=ER2 (E=Si, Ge, Sn, Pb) substituted by multiple N/P/O/S-donor groups are extremely rare due to their propensity to disaggregate into their tetrylene monomers R2E. We report the synthesis of the first fully phosphanyl-substituted digermene {(Mes)2P}2Ge=Ge{P(Mes)2}2 (3, Mes=2,4,6-Me3C6H2), which adopts a highly unusual structure in the solid state, that is both strongly trans-bent and highly twisted. Variable-temperature 31P{1H} NMR spectroscopy suggests that 3 persists in solution, but is subject to a dynamic equilibrium between two conformations, which have different geometries about the Ge=Ge bond (twisted/non-twisted) due to a difference in the nature of their π-stacking interactions. Compound 3 undergoes unprecedented, spontaneous decomposition in solution to give a unique GeI cluster {(Mes)2P}4Ge4⋅5 CyMe (7).

Publication metadata

Author(s): Izod K, Liu M, Evans P, Wills C, Dixon CM, Waddell PG, Probert MR

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie - International Edition

Year: 2022

Volume: 61

Issue: 39

Print publication date: 19/09/2022

Online publication date: 25/08/2022

Acceptance date: 10/08/2022

Date deposited: 18/10/2022

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: John Wiley and Sons Inc

URL: https://doi.org/10.1002/anie.202208851

DOI: 10.1002/anie.202208851

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