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

Synthesis and characterisation of transition metal omplexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine
Synthesis and characterisation of transition metal omplexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine
The one‐step synthesis (44% isolated yield) of the 1,5‐benzodiazapine functionalised phosphine 1 , C 31 H 31 N 2 OP, is reported. Bridge cleavage of {MCl(μ‐Cl)(η 5 ‐Cp*)} 2 (M = Ir, Rh) with 2 equiv. of 1 in CH 2 Cl 2 gave the mononuclear compounds [MCl 2 (η 5 ‐Cp*)( P‐ 1 )] (M = Ir, 2a ; M = Rh, 2b ) in which 1 functions as a P ‐monodentate ligand. Rapid C(sp 3 )‐H bond activation, at room temperature, is observed for 2a leading to the unusual cyclometallated complex [Ir(η 5 ‐Cp*)( P,N,C‐ 1 )]Cl 2 3 (or 3` ) bearing an anionic P / N amine / C ‐terdentate ligand. Reaction of [Pt(CH 3 )Cl(η 4 ‐cod)] with one equiv. of 1 led to [Pt(CH 3 )Cl( P,N ‐ 1 )] 4 suggesting that 3 may proceed through formation of an intermediate Ir III cationic species in which the ligand is P,N ‐bound. The Ir I complex [IrCl(η 4 ‐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.
1,5-benzodiazapines, phosphine ligands, late- transition metals, X-ray diffraction, CH activation
1434-1948
Durran, Sean E.
025c7e81-13d2-4b41-9353-a97b00f3f93d
Elsegood, Mark R.J.
cd443b3b-44f9-461c-8310-a885eb86a44e
Noble, Thomas A.
2ee10717-b314-4035-be95-abbfe57a86bf
Smith, Martin B.
bc6e6c8e-8c15-44a8-84fa-2fe923ba21f8
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, Michael
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Durran, Sean E.
025c7e81-13d2-4b41-9353-a97b00f3f93d
Elsegood, Mark R.J.
cd443b3b-44f9-461c-8310-a885eb86a44e
Noble, Thomas A.
2ee10717-b314-4035-be95-abbfe57a86bf
Smith, Martin B.
bc6e6c8e-8c15-44a8-84fa-2fe923ba21f8
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, Michael
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161

Durran, Sean E., Elsegood, Mark R.J., Noble, Thomas A., Smith, Martin B., Gelbrich, Thomas, Hursthouse, Michael and Light, Mark (2021) Synthesis and characterisation of transition metal omplexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine. European Journal of Inorganic Chemistry. (doi:10.1002/ejic.202100236). (In Press)

Record type: Article

Abstract

The one‐step synthesis (44% isolated yield) of the 1,5‐benzodiazapine functionalised phosphine 1 , C 31 H 31 N 2 OP, is reported. Bridge cleavage of {MCl(μ‐Cl)(η 5 ‐Cp*)} 2 (M = Ir, Rh) with 2 equiv. of 1 in CH 2 Cl 2 gave the mononuclear compounds [MCl 2 (η 5 ‐Cp*)( P‐ 1 )] (M = Ir, 2a ; M = Rh, 2b ) in which 1 functions as a P ‐monodentate ligand. Rapid C(sp 3 )‐H bond activation, at room temperature, is observed for 2a leading to the unusual cyclometallated complex [Ir(η 5 ‐Cp*)( P,N,C‐ 1 )]Cl 2 3 (or 3` ) bearing an anionic P / N amine / C ‐terdentate ligand. Reaction of [Pt(CH 3 )Cl(η 4 ‐cod)] with one equiv. of 1 led to [Pt(CH 3 )Cl( P,N ‐ 1 )] 4 suggesting that 3 may proceed through formation of an intermediate Ir III cationic species in which the ligand is P,N ‐bound. The Ir I complex [IrCl(η 4 ‐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.

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More information

Accepted/In Press date: 28 April 2021
Keywords: 1,5-benzodiazapines, phosphine ligands, late- transition metals, X-ray diffraction, CH activation

Identifiers

Local EPrints ID: 449114
URI: http://eprints.soton.ac.uk/id/eprint/449114
ISSN: 1434-1948
PURE UUID: 0a44e6b2-9056-4d5d-88c7-6ff3f9822232
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 17 May 2021 16:33
Last modified: 18 May 2021 01:37

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