Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3) |
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| Authors: | Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Klaus Dück Dr. Marco Fuß Dr. Christian Hörl Dr. Thomas Kramer Dr. Ivo Krummenacher Dr. Thomas Kupfer Valerie Paprocki Christoph Schneider |
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| Affiliation: | Institut für Anorganische Chemie, Julius‐Maximilians‐Universit?t Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49)?931‐31‐84623 |
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| Abstract: | We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the Cipso?Sn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred. |
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| Keywords: | ansa‐complexes manganese sandwich complexes synthetic methods |
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