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Halterman corroles and their use as a probe of the conformational dynamics of the inherently chiral copper corrole chromophore

Halterman corroles and their use as a probe of the conformational dynamics of the inherently chiral copper corrole chromophore
Halterman corroles and their use as a probe of the conformational dynamics of the inherently chiral copper corrole chromophore

Halterman corroles have been synthesized for the first time from pyrrole and Halterman's aldehyde via Gryko's "water-methanol method". These were derivatized to the corresponding copper complexes and subsequently to the β-octabromo complexes. Electronic circular dichroism spectra were recorded for the enantiopure copper complexes, affording the first such measurements for the inherently chiral Cu corrole chromophore. Interestingly, for a given configuration of the Halterman substituents, X-ray crystallographic studies revealed both P and M conformations of the Cu-corrole core, proving that the substituents, even in conjunction with β-octabromination, are unable to lock the Cu-corrole core into a given chirality. The overall body of evidence strongly indicates a dynamic equilibrium between the P and M conformations. Such an interconversion, which presumably proceeds via saddling inversion, provides a rationale for our failure so far to resolve sterically hindered Cu corroles into their constituent enantiomers by means of chiral HPLC.

0020-1669
4270-4276
Thomas, Kolle E.
b79e1c79-5c1e-46b5-a4b5-f82bb02a927d
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Carrié, Daniel
64538f13-f8bd-452e-9e2e-a61cdc4318b7
Vazquez-Lima, Hugo
e33ec9ee-1df4-4633-a970-eb464b54aa2f
Simonneaux, Gérard
0bc2b2fa-b5b8-4f27-98e0-d50b54f54727
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7
Thomas, Kolle E.
b79e1c79-5c1e-46b5-a4b5-f82bb02a927d
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Carrié, Daniel
64538f13-f8bd-452e-9e2e-a61cdc4318b7
Vazquez-Lima, Hugo
e33ec9ee-1df4-4633-a970-eb464b54aa2f
Simonneaux, Gérard
0bc2b2fa-b5b8-4f27-98e0-d50b54f54727
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7

Thomas, Kolle E., McCormick, Laura J., Carrié, Daniel, Vazquez-Lima, Hugo, Simonneaux, Gérard and Ghosh, Abhik (2018) Halterman corroles and their use as a probe of the conformational dynamics of the inherently chiral copper corrole chromophore. Inorganic Chemistry, 57 (8), 4270-4276. (doi:10.1021/acs.inorgchem.7b02767).

Record type: Article

Abstract

Halterman corroles have been synthesized for the first time from pyrrole and Halterman's aldehyde via Gryko's "water-methanol method". These were derivatized to the corresponding copper complexes and subsequently to the β-octabromo complexes. Electronic circular dichroism spectra were recorded for the enantiopure copper complexes, affording the first such measurements for the inherently chiral Cu corrole chromophore. Interestingly, for a given configuration of the Halterman substituents, X-ray crystallographic studies revealed both P and M conformations of the Cu-corrole core, proving that the substituents, even in conjunction with β-octabromination, are unable to lock the Cu-corrole core into a given chirality. The overall body of evidence strongly indicates a dynamic equilibrium between the P and M conformations. Such an interconversion, which presumably proceeds via saddling inversion, provides a rationale for our failure so far to resolve sterically hindered Cu corroles into their constituent enantiomers by means of chiral HPLC.

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More information

e-pub ahead of print date: 2 April 2018
Published date: 16 April 2018

Identifiers

Local EPrints ID: 439030
URI: http://eprints.soton.ac.uk/id/eprint/439030
ISSN: 0020-1669
PURE UUID: d15cd9e6-d166-46f8-8e39-d0819d87b25d
ORCID for Laura J. McCormick: ORCID iD orcid.org/0000-0002-6634-4717

Catalogue record

Date deposited: 01 Apr 2020 16:32
Last modified: 16 Sep 2021 11:14

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Contributors

Author: Kolle E. Thomas
Author: Daniel Carrié
Author: Hugo Vazquez-Lima
Author: Gérard Simonneaux
Author: Abhik Ghosh

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