Mede Ralf, Lorett-Velásquez Vaneza Paola, Klein Moritz, Görls Helmar, Schmitt Michael, Gessner Guido, Heinemann Stefan H, Popp Jürgen, Westerhausen Matthias
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstraße 8, D-07743 Jena, Germany.
Dalton Trans. 2015 Feb 21;44(7):3020-33. doi: 10.1039/c4dt03567d.
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).
通过Mn2(CO)10与二芳基二硫醚的反应或[(OC)5MnBr]与芳硫醇的反应，制备了几种[(OC)4Mn(μ-SR)]2类型的苯硫醇锰羰基配合物（R = Ph ()、C6H4-4-CH3 ()、C6H4-4-CF3 ()、C6H4-4-F ()、C6H4-4-Cl ()、C6H4-4-OMe ()、C6F5 () 和CH2C6H4-4-Cl ()）。这些配合物很容易失去两个一氧化碳分子，生成四核[(OC)3Mn(μ3-SR)]4 ()。含氟取代芳基的衍生物通常形成双核和四核的混合物，通过加热相应的反应混合物可将其定量转化为 。发现均三甲苯基衍生物[(OC)4Mn(μ-SMes)]3 ()具有独特的三核结构，红外光谱和核磁共振光谱证实该结构在溶液中保持稳定。已对痕量的已知双核副产物[(OC)3Mn(μ-SC6H3(-4-Me)-2-SC6H4-4-Me)]2 ()进行了结构表征。研究了[(OC)4Mn(μ-SPh)]2 ()作为一氧化碳释放分子（CORM）用于一氧化碳给药的适用性。将其溶解在强路易斯碱性溶剂L中时会释放出两个一氧化碳分子，生成[(OC)3Mn(L)(μ-SPh)]2，该产物在光照下会释放出所有剩余的一氧化碳分子（光CORM行为）。
