title: 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 (), C6H4-4-CH3 (), C6H4-4-CF3 (), C6H4-4-F (), C6H4-4-Cl (), C6H4-4-OMe (), C6F5 (), and CH2C6H4-4-Cl ()) 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 (). Derivatives with fluoro-substituted aryl groups commonly form mixtures of dinuclear and tetranuclear which can quantitatively be converted to by heating of the corresponding reaction mixtures. A unique trinuclear structure is found for the mesityl derivative [(OC)4Mn(μ-SMes)]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 () have been structurally characterized. The suitability of [(OC)4Mn(μ-SPh)]2 () 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).
authors.affiliation: Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstraße 8, D-07743 Jena, Germany. m.we@uni-jena.de.
authors.forename: Ralf
authors.initials: R
authors.lastname: Mede
authors.forename: Vaneza Paola
authors.initials: VP
authors.lastname: Lorett-Velásquez
authors.forename: Moritz
authors.initials: M
authors.lastname: Klein
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.forename: Guido
authors.initials: G
authors.lastname: Gessner
authors.forename: Stefan H
authors.initials: SH
authors.lastname: Heinemann
authors.forename: Jürgen
authors.initials: J
authors.lastname: Popp
authors.forename: Matthias
authors.initials: M
authors.lastname: Westerhausen
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry / Q000378:metabolism*; D018360:Crystallography, X-Ray; D008345:Manganese / Q000737:chemistry / Q000378:metabolism*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry / Q000378:metabolism*; D013438:Sulfhydryl Compounds / Q000737:chemistry / Q000378:metabolism*
chemical_list: D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D008345:Manganese; D002248:Carbon Monoxide