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Issue 43, 2016
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Light- or oxidation-triggered CO release from [MnI(CO)33-L)] complexes: reaction intermediates and a new synthetic route to [MnIII/IV2(μ-O)2(L)2] compounds

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Abstract

The reaction products and intermediates of the three CO-releasing manganese(I) coordination compounds [Mn(tpm)(CO)3]+, [Mn(bpza)(CO)3] and [Mn(tpa)(CO)3]+ were analysed by combining IR-spectroscopy, electrochemical measurements and single-crystal XRD. The intermediate formation of manganese(I) biscarbonyl compounds and the rather facile oxidation of these species were identified as key reaction steps that accompany CO liberation. For the use of [MnI(CO)3] complexes as light-triggered CO sources, the results indicate that in this case photo- and redox-chemistry seem to be strongly coupled which could be important and potentially even useful in the pharmacological context. Additionally, one has to be aware of the fact that [MnII3-L)(solv)3]2+ complexes, the primary reaction products after CO substitution, are able to bind to proteins, which was demonstrated using bovine serum albumin as a model. And finally it could be shown that the CO-release reactions can be used as a new synthetic route to prepare multinuclear μ-oxido-bridged manganese complexes: the mixed-valence compound [MnIII/IV2(μ-O)2(tpa)2]3+ could be prepared in a single step from [Mn(tpa)(CO)3]+via photo- or electrochemically induced CO substitution.

Graphical abstract: Light- or oxidation-triggered CO release from [MnI(CO)3(κ3-L)] complexes: reaction intermediates and a new synthetic route to [MnIII/IV2(μ-O)2(L)2] compounds

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Publication details

The article was received on 20 May 2016, accepted on 06 Oct 2016 and first published on 07 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT02020H
Citation: Dalton Trans., 2016,45, 17464-17473
  • Open access: Creative Commons BY license
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    Light- or oxidation-triggered CO release from [MnI(CO)33-L)] complexes: reaction intermediates and a new synthetic route to [MnIII/IV2(μ-O)2(L)2] compounds

    U. Sachs, G. Schaper, D. Winkler, D. Kratzert and P. Kurz, Dalton Trans., 2016, 45, 17464
    DOI: 10.1039/C6DT02020H

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