The University of Southampton
University of Southampton Institutional Repository

Structural diversity in the first metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles

Structural diversity in the first metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles
Structural diversity in the first metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles
Metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles have been structurally characterised for the first time, complementing the significant amount of work that has been reported for the analogous pyridine ligands. N,N-Bis(3,5-dinitrophenyl)-3,4-diphenyl-1H-pyrrole-2,5-dicarboxamide forms octahedral bis(tridentate) complexes with cobalt(III) and nickel(II), where the ligands are bound to the metal centres through deprotonated pyrrole and amide N atoms. N,N-Dibutyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide and N,N-diphenyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide also form bis(tridentate) cobalt complexes but are only deprotonated at the pyrrole N atom, the remainder of the coordination sphere comprising the thioamide S atoms. The dibutyl derivative was isolated as a Co(II) complex, whereas the diphenyl system deposited a Co(III) complex. In contrast, N,N-dibutyl-3,4-dichloro-1H-pyrrole-2,5-dicarboxamide was found to act as a bidentate ligand, in an octahedral cobalt(II) complex comprising of two bidentate pyrrole ligands, and two aqua ligands. Synthesis of N,N-bis(pyridin-2-ylmethyl)-3,4-diphenyl-1H-pyrrole-2,5-carboxamide gave a pyrrole ligand with increased denticity. Reaction with cobalt(II) chloride resulted in the isolation of a dinuclear helicate complex. The ligand was found to have undergone addition of a methoxy group to one of the linking methylene carbons, presumably as a result of the oxidative addition of solvent methanol.
0300-9246
4106-4112
Bates, Gareth W.
784ac62e-67f5-400a-ab9a-42615be9ec9d
Gale, Philip A.
c840b7e9-6847-4843-91af-fa0f8563d943
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Ogden, Mark I.
1461a54b-2593-4f78-98f3-69e77c316903
Warriner, Colin N.
2cdda67a-3408-4a5e-963c-8b0ee7555980
Bates, Gareth W.
784ac62e-67f5-400a-ab9a-42615be9ec9d
Gale, Philip A.
c840b7e9-6847-4843-91af-fa0f8563d943
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Ogden, Mark I.
1461a54b-2593-4f78-98f3-69e77c316903
Warriner, Colin N.
2cdda67a-3408-4a5e-963c-8b0ee7555980

Bates, Gareth W., Gale, Philip A., Light, Mark E., Ogden, Mark I. and Warriner, Colin N. (2008) Structural diversity in the first metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles. Dalton Transactions, (31), 4106-4112. (doi:10.1039/b802506a).

Record type: Article

Abstract

Metal complexes of 2,5-dicarboxamidopyrroles and 2,5-dicarbothioamidopyrroles have been structurally characterised for the first time, complementing the significant amount of work that has been reported for the analogous pyridine ligands. N,N-Bis(3,5-dinitrophenyl)-3,4-diphenyl-1H-pyrrole-2,5-dicarboxamide forms octahedral bis(tridentate) complexes with cobalt(III) and nickel(II), where the ligands are bound to the metal centres through deprotonated pyrrole and amide N atoms. N,N-Dibutyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide and N,N-diphenyl-3,4-diphenyl-1H-pyrrole-2,5-dicarboxthioamide also form bis(tridentate) cobalt complexes but are only deprotonated at the pyrrole N atom, the remainder of the coordination sphere comprising the thioamide S atoms. The dibutyl derivative was isolated as a Co(II) complex, whereas the diphenyl system deposited a Co(III) complex. In contrast, N,N-dibutyl-3,4-dichloro-1H-pyrrole-2,5-dicarboxamide was found to act as a bidentate ligand, in an octahedral cobalt(II) complex comprising of two bidentate pyrrole ligands, and two aqua ligands. Synthesis of N,N-bis(pyridin-2-ylmethyl)-3,4-diphenyl-1H-pyrrole-2,5-carboxamide gave a pyrrole ligand with increased denticity. Reaction with cobalt(II) chloride resulted in the isolation of a dinuclear helicate complex. The ligand was found to have undergone addition of a methoxy group to one of the linking methylene carbons, presumably as a result of the oxidative addition of solvent methanol.

Full text not available from this repository.

More information

Published date: August 2008

Identifiers

Local EPrints ID: 144963
URI: https://eprints.soton.ac.uk/id/eprint/144963
ISSN: 0300-9246
PURE UUID: 738ac81c-789e-49db-8dca-575af8250984
ORCID for Philip A. Gale: ORCID iD orcid.org/0000-0001-9751-4910
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 15 Apr 2010 13:25
Last modified: 20 Jul 2019 01:10

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of https://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×