ejic.202100236.pdf (1.25 MB)
Synthesis and characterisation of transition metal complexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine
journal contribution
posted on 2021-05-20, 13:41 authored by Sean E. Durran, Mark ElsegoodMark Elsegood, Thomas A. Noble, Martin SmithMartin Smith, Thomas Gelbrich, Michael B Hursthouse, Mark E LightThe 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 ChemistryVolume
2021Issue
23Pages
2274-2280Publisher
WileyVersion
- VoR (Version of Record)
Rights holder
© The authorsPublisher 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
2021-04-28Publication date
2021-05-17Copyright date
2021ISSN
1434-1948eISSN
1099-0682Publisher version
Language
- en