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Mild intramolecular P–C(sp3) bond cleavage in bridging diphosphine complexes of RuII RhIII and IrIII

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journal contribution
posted on 2022-12-07, 13:44 authored by Peter De'Ath, Mark ElsegoodMark Elsegood, Christopher Halliwell, Martin SmithMartin Smith

Three new carboxylic acid functionalised diphosphines, R2PCH2N(Ar)CH2PR2 [CyL1 R = Cy, Ar = (1-CO2H)(3-OMe)C6H3, CyL2R = Cy, Ar = (1-CO2H)(3-OH)C6H3 and PhL3 R = Ph, Ar = (1-CO2H)(5-OMe)C6H3] have been prepared from condensation of R2PCH2OH and the appropriate aromatic amine in MeOH, and isolated as colourless solids (for CyL1, CyL2) in good yield. Reaction of CyL1, CyL2, or PhL3, along with the previously reported diphosphines PhL1, PhL2, and PhL4, and [RuCl(μ-Cl)(η6-Me2CHC6H4Me)]2 in CH2Cl2 affords the P/P-bridging dinuclear ruthenium(II) complexes {RuCl2(η6-Me2CHC6H4Me)}2(μ-CyL1PhL4) 1af as red/orange solids. Careful monitoring by 31P{1H} NMR spectroscopy of CDCl3 solutions of 1ae revealed remarkably clean P−Csp3 bond cleavage to give RuII mononuclear species 2ae and the known secondary phosphine complexes RuCl26-Me2CHC6H4Me)(PCy2H) 3 and RuCl26-Me2CHC6H4Me)(PPh2H) 4. Furthermore, facile P−Csp3 bond cleavage of PhL1 can be observed using the chloro-bridged dimers [IrCl(μ-Cl)(η5-C5Me5)]2 or [RhCl(μ-Cl)(η5-C5Me5)]2 instead. Deuterium labelling of CyL1CyL1PhL1, and PhL2 enabled the assignment of the methylene protons to be confirmed from 1H NMR spectroscopy. All new compounds have been characterised using a range of spectroscopic and analytical techniques. Single crystal X-ray structures have been determined for CyL1, 1d·3OEt2, 1f·2CDCl3·OEt2, 2b, 2c, 2d·CDCl3, 2e·0.5OEt2 and 6b·1.5CDCl3. The free phenolic group in CyL1, 1d·3OEt2, 1f·2CDCl3·OEt2, 2b and 2d·CDCl3 participates in intra- or intermolecular O−H···O hydrogen bonding. 

Funding

EPSRC Centre for Doctoral Training in Embedded Intelligence

Engineering and Physical Sciences Research Council

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History

School

  • Science

Department

  • Chemistry

Published in

Journal of Organometallic Chemistry

Volume

937

Issue

2021

Publisher

Elsevier

Version

  • AM (Accepted Manuscript)

Rights holder

© Elsevier

Publisher statement

This paper was accepted for publication in the Journal of Organometallic Chemistry and the definitive published version is available at https://doi.org/10.1016/j.jorganchem.2021.121704

Acceptance date

2021-01-10

Publication date

2021-01-16

Copyright date

2021

ISSN

0022-328X

Language

  • en

Depositor

Dr Martin Smith. Deposit date: 2 December 2022

Article number

121704

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