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Remote Substituent Effects on the Structures and Stabilities of P=E π-Stabilized Diphosphatetrylenes (R₂P)₂E (E = Ge, Sn)

Lookup NU author(s): Dr Keith IzodORCiD, Dr Peter Evans, Dr Paul Waddell, Professor Mike ProbertORCiD

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Abstract

A rare P-E π-interaction between the lone pair of a planar phosphorus center and the vacant p-orbital at the germanium or tin center provides efficient stabilization for phosphorus-substituted tetrylenes (R₂P)₂E [E = Ge, Sn] and enables the isolation of the first example of a compound with a crystallographically authenticated P=Sn bond. Subtle changes in the electronic properties of the bulky aryl substituents in these compounds change the preference for planar versus pyramidal phosphorus centers in the solid state; however, variable-temperature NMR spectroscopy indicates that in solution these species are subject to a dynamic equilibrium which interconverts the planar and pyramidal phosphorus centers. Consistent with this, DFT studies suggest that there is only a small energy difference between the planar and pyramidal forms of these compounds and reveal a small singlet-triplet energy separation, suggesting potentially interesting reactivities.

Publication metadata

Author(s): Izod K, Evans P, Waddell PG, Probert MR

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2016

Volume: 55

Issue: 20

Pages: 10510-10522

Online publication date: 30/09/2016

Acceptance date: 22/09/2016

Date deposited: 22/09/2016

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: Americal Chemical Society

URL: http://dx.doi.org/10.1021/acs.inorgchem.6b01566

DOI: 10.1021/acs.inorgchem.6b01566

Data Access Statement: http://dx.doi.org/10.17634/154300-31

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