Issue 7, 2015

Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(i) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2

Abstract

Several phenylthiolatomanganese carbonyl complexes of the type [(OC)4Mn(μ-SR)]2 (R = Ph (1a), C6H4-4-CH3 (1b), C6H4-4-CF3 (1c), C6H4-4-F (1d), C6H4-4-Cl (1e), C6H4-4-OMe (1f), C6F5 (1g), and CH2C6H4-4-Cl (1h)) have been prepared via the reaction of Mn2(CO)10 with diaryldisulfane or via the reaction of [(OC)5MnBr] with arylthiols. These complexes lose two carbon monoxide molecules quite easily yielding tetranuclear [(OC)3Mn(μ3-SR)]4 (2). Derivatives with fluoro-substituted aryl groups commonly form mixtures of dinuclear 1 and tetranuclear 2 which can quantitatively be converted to 2 by heating of the corresponding reaction mixtures. A unique trinuclear structure is found for the mesityl derivative [(OC)4Mn(μ-SMes)]3 (3) which is maintained in solution as verified by IR and NMR spectroscopy. Traces of an already known dinuclear by-product of the type [(OC)3Mn(μ-SC6H3(-4-Me)-2-SC6H4-4-Me)]2 (4) have been structurally characterized. The suitability of [(OC)4Mn(μ-SPh)]2 (1a) as a CO releasing molecule (CORM) for the administration of carbon monoxide has been studied. Two CO molecules are released upon dissolving in strongly Lewis basic solvents L, yielding [(OC)3Mn(L)(μ-SPh)]2, which liberates all the remaining CO molecules upon irradiation (photoCORM behavior).

Graphical abstract: Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(i) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2

Supplementary files

Article information

Article type
Paper
Submitted
20 Nov 2014
Accepted
17 Dec 2014
First published
18 Dec 2014

Dalton Trans., 2015,44, 3020-3033

Carbon monoxide release properties and molecular structures of phenylthiolatomanganese(I) carbonyl complexes of the type [(OC)4Mn(μ-S-aryl)]2

R. Mede, V. P. Lorett-Velásquez, M. Klein, H. Görls, M. Schmitt, G. Gessner, S. H. Heinemann, J. Popp and M. Westerhausen, Dalton Trans., 2015, 44, 3020 DOI: 10.1039/C4DT03567D

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