Redox-tagged carbon monoxide-releasing molecules (CORMs): Ferrocene-containing [Mn(C^N)(CO)4] complexes as a promising new CORM class

Benjamin James Aucott; Jonathan Stuart Ward; Samuel Andrew; Jessica Milani; Adrian C. Whitwood; Jason Martin Lynam; Alison Parkin; Ian James Stewart Fairlamb

doi:10.1021/acs.inorgchem.7b00509

Redox-tagged carbon monoxide-releasing molecules (CORMs): Ferrocene-containing [Mn(C^N)(CO)4] complexes as a promising new CORM class

Benjamin James Aucott, Jonathan Stuart Ward, Samuel Andrew, Jessica Milani, Adrian C. Whitwood, Jason Martin Lynam, Alison Parkin, Ian James Stewart Fairlamb

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

This study describes the synthesis and characterization of a new class of ferrocene-containing carbon monoxide-releasing molecules (CORMs, 1-3). The ferrocenyl group is both a recognized therapeutically viable co-ligand and a handle for informative infrared spectroelectrochemistry. Deoxy-myoglobin CO-release assays and in situ infrared spectroscopy confirm compounds 2 and 3 as photoCORMs and 1 as a thermal CORM, attributed to the increased sensitivity of the Mn-ferrocenyl bond to protonation in 1. Electrochemical and infrared spectroelectrochemical experiments confirm a single reversible redox couple associated with the ferrocenyl moiety with the Mn tetracarbonyl center showing no redox activity up to +590 mV vs Fc/Fc+, though no concomitant CO release was observed in association with the redox activity. The effects of linker length on communication between the Fe and Mn centers suggest the incorporation of redox-active ligands into CORMs focus on the first coordination sphere of the CORM. Redox-tagged CORMs could prove to be a useful mechanistic probe; our findings could be developed to use redox changes to trigger CO-release.

Original language	English
Pages (from-to)	5431 − 5440
Number of pages	10
Journal	Inorganic Chemistry
Volume	56
DOIs	https://doi.org/10.1021/acs.inorgchem.7b00509
Publication status	Published - 19 Apr 2017

Bibliographical note

© 2017 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

Keywords

Carbon Monoxide
CO-RMs
CORM
Drug
Mechanism
MANGANESE

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Cite this

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title = "Redox-tagged carbon monoxide-releasing molecules (CORMs): Ferrocene-containing [Mn(C^N)(CO)4] complexes as a promising new CORM class",

abstract = "This study describes the synthesis and characterization of a new class of ferrocene-containing carbon monoxide-releasing molecules (CORMs, 1-3). The ferrocenyl group is both a recognized therapeutically viable co-ligand and a handle for informative infrared spectroelectrochemistry. Deoxy-myoglobin CO-release assays and in situ infrared spectroscopy confirm compounds 2 and 3 as photoCORMs and 1 as a thermal CORM, attributed to the increased sensitivity of the Mn-ferrocenyl bond to protonation in 1. Electrochemical and infrared spectroelectrochemical experiments confirm a single reversible redox couple associated with the ferrocenyl moiety with the Mn tetracarbonyl center showing no redox activity up to +590 mV vs Fc/Fc+, though no concomitant CO release was observed in association with the redox activity. The effects of linker length on communication between the Fe and Mn centers suggest the incorporation of redox-active ligands into CORMs focus on the first coordination sphere of the CORM. Redox-tagged CORMs could prove to be a useful mechanistic probe; our findings could be developed to use redox changes to trigger CO-release.",

keywords = "Carbon Monoxide, CO-RMs, CORM, Drug, Mechanism, MANGANESE",

author = "Aucott, {Benjamin James} and Ward, {Jonathan Stuart} and Samuel Andrew and Jessica Milani and Whitwood, {Adrian C.} and Lynam, {Jason Martin} and Alison Parkin and Fairlamb, {Ian James Stewart}",

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doi = "10.1021/acs.inorgchem.7b00509",

language = "English",

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T1 - Redox-tagged carbon monoxide-releasing molecules (CORMs): Ferrocene-containing [Mn(C^N)(CO)4] complexes as a promising new CORM class

AU - Aucott, Benjamin James

AU - Ward, Jonathan Stuart

AU - Andrew, Samuel

AU - Milani, Jessica

AU - Whitwood, Adrian C.

AU - Lynam, Jason Martin

AU - Parkin, Alison

AU - Fairlamb, Ian James Stewart

N1 - © 2017 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2017/4/19

Y1 - 2017/4/19

N2 - This study describes the synthesis and characterization of a new class of ferrocene-containing carbon monoxide-releasing molecules (CORMs, 1-3). The ferrocenyl group is both a recognized therapeutically viable co-ligand and a handle for informative infrared spectroelectrochemistry. Deoxy-myoglobin CO-release assays and in situ infrared spectroscopy confirm compounds 2 and 3 as photoCORMs and 1 as a thermal CORM, attributed to the increased sensitivity of the Mn-ferrocenyl bond to protonation in 1. Electrochemical and infrared spectroelectrochemical experiments confirm a single reversible redox couple associated with the ferrocenyl moiety with the Mn tetracarbonyl center showing no redox activity up to +590 mV vs Fc/Fc+, though no concomitant CO release was observed in association with the redox activity. The effects of linker length on communication between the Fe and Mn centers suggest the incorporation of redox-active ligands into CORMs focus on the first coordination sphere of the CORM. Redox-tagged CORMs could prove to be a useful mechanistic probe; our findings could be developed to use redox changes to trigger CO-release.

AB - This study describes the synthesis and characterization of a new class of ferrocene-containing carbon monoxide-releasing molecules (CORMs, 1-3). The ferrocenyl group is both a recognized therapeutically viable co-ligand and a handle for informative infrared spectroelectrochemistry. Deoxy-myoglobin CO-release assays and in situ infrared spectroscopy confirm compounds 2 and 3 as photoCORMs and 1 as a thermal CORM, attributed to the increased sensitivity of the Mn-ferrocenyl bond to protonation in 1. Electrochemical and infrared spectroelectrochemical experiments confirm a single reversible redox couple associated with the ferrocenyl moiety with the Mn tetracarbonyl center showing no redox activity up to +590 mV vs Fc/Fc+, though no concomitant CO release was observed in association with the redox activity. The effects of linker length on communication between the Fe and Mn centers suggest the incorporation of redox-active ligands into CORMs focus on the first coordination sphere of the CORM. Redox-tagged CORMs could prove to be a useful mechanistic probe; our findings could be developed to use redox changes to trigger CO-release.

KW - Carbon Monoxide

KW - CO-RMs

KW - CORM

KW - Drug

KW - Mechanism

KW - MANGANESE

U2 - 10.1021/acs.inorgchem.7b00509

DO - 10.1021/acs.inorgchem.7b00509

M3 - Article

VL - 56

SP - 5431 − 5440

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -