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Synthesis and characterisation of transition metal complexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine

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journal contribution
posted on 20.05.2021, 13:41 by Sean E. Durran, Mark Elsegood, Thomas A. Noble, Martin Smith, Thomas Gelbrich, Michael B Hursthouse, Mark E Light
The one-step synthesis (44% isolated yield) of the 1,5- benzodiazapine functionalised phosphine 1, C31H31N2OP, is reported. Bridge cleavage of {MCl(μ-Cl)(η5 -Cp*)}2 (M=Ir, Rh) with 2 equiv. of 1 in CH2Cl2 gave the mononuclear compounds [MCl2(η5 -Cp*)(P-1)] (M=Ir, 2a; M=Rh, 2b) in which 1 functions as a P-monodentate ligand. Rapid C(sp3 ) H bond activation, at room temperature, is observed for 2a leading to the unusual cyclometallated complex [Ir(η5 -Cp*)(P,N,C-1)]Cl2 3 (or 3‘) bearing an anionic P/Namine/C-terdentate ligand. Reaction of [Pt(CH3) Cl(η4 -cod)] with one equiv. of 1 led to [Pt(CH3)Cl(P,N-1)] 4, suggesting that 3 may form via an intermediate IrIII cationic species in which the ligand is P,N-bound. The IrI complex [IrCl (η4 -cod)(P-1)] 5 does not, under similar conditions, show any evidence for C H activation. Single crystal X-ray studies on 1, 2a, 2b, 3, 3‘, 4, and 5 reveal intramolecular N···H O H-bonding in all cases.

Funding

EPSRC Studentship

History

School

  • Science

Department

  • Chemistry

Published in

European Journal of Inorganic Chemistry

Volume

2021

Issue

23

Pages

2274-2280

Publisher

Wiley

Version

VoR (Version of Record)

Rights holder

© The authors

Publisher statement

This is an Open Access Article. It is published by Wiley under the Creative Commons Attribution 4.0 Unported Licence (CC BY). Full details of this licence are available at: http://creativecommons.org/licenses/by/4.0/

Acceptance date

28/04/2021

Publication date

2021-05-17

Copyright date

2021

ISSN

1434-1948

eISSN

1099-0682

Language

en

Depositor

Deposit date: 20 May 2021