Toggle Main Menu Toggle Search

Open Access padlockePrints

P-Ge/Sn π interactions Versus Arene···Ge/Sn Contacts for the Stabilization of Diphosphatetrylenes, (R2P)2E (E = Ge, Sn)

Lookup NU author(s): Dr Keith Izod, Dr Paul Waddell

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

© 2019 American Chemical Society.The diphosphatetrylenes {(Dipp)(R′)P}2E [R′ = Mes, E = Ge (1Ge), Sn (1Sn); R′ = CH(SiMe3)2, E = Sn (2Sn)] have been isolated and characterized by multinuclear and variable temperature NMR spectroscopy and X-ray crystallography [Dipp = 2,6-iPr2C6H3, Mes = 2,4,6-Me3C6H2]. All three compounds crystallize as discrete monomers with two pyramidal phosphorus centers. However, variable-temperature 31P{1H} NMR spectroscopy indicates that both 1Ge and 2Sn are subject to dynamic exchange between this form and a form containing one planar and one pyramidal phosphorus center in solution. In contrast, 1Sn retains two pyramidal phosphorus centers in solution and exhibits no evidence for exchange with a form containing a planar phosphorus center. The related compound [{(Me3Si)2CH}2P]2Sn (3Sn) was isolated in very low yield and was shown by X-ray crystallography to possess one planar and one pyramidal phosphorus center in the solid state. DFT calculations reveal that the conformations of 1Ge, 1Sn, and 2Sn observed in the solid state are significantly stabilized by the delocalization of electron density from the aromatic rings into the vacant p-orbital at the tetrel center. Thus, for diphosphatetrylenes possessing aromatic substituents at phosphorus, stabilization may be achieved by two competing mechanisms: (i) planarization of one phosphorus center and consequent delocalization of the phosphorus lone pair into the vacant tetrel p-orbital or (ii) pyramidalization of both phosphorus centers and delocalization of aromatic π-electron density into the tetrel p-orbital. For 3Sn, which lacks aromatic groups, only the former stabilization mechanism is possible.


Publication metadata

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

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2020

Volume: 59

Issue: 1

Pages: 863-874

Print publication date: 06/01/2020

Online publication date: 19/12/2019

Acceptance date: 02/04/2019

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society

URL: https://doi.org/10.1021/acs.inorgchem.9b03109

DOI: 10.1021/acs.inorgchem.9b03109


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share