Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen: XVII. Selen- und tellur-brücken in organometallkomplexen: AUFBAU,protonierung und methylierung |
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| Authors: | Wolfgang A Herrmann Jürgen Rohrmann Christian Hecht |
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| Institution: | Institut für Anorganische Chemie der Johann Wolfgang Goethe-Universität, Niederurseler Hang, D-6000 Frankfurt am Main 50 Deutschland |
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| Abstract: | Selenium acts as a bridging ligand between two iron atoms in the novel complex (μ-Se)(η5-C5H5)Fe(CO)2]2 (1), obtained in 60% yield from Na+(η5-C5H5)Fe(CO)2] and Se2Cl2. 1 displays nucleophilic reactivity towards protic acids (e.g., HBF4·OEt2) and methyl triflate, CF3SO3CH3, thus giving the protonated and methylated ionic species (μ-SeR)(η5-C5H5)Fe(CO)22]+ (R = H: 2a, BF4 salt; R = CH3: 2b, PF6 salt) in quantitative yields. Rapid deprotonation of 2a occurs in the presence of bases such as diethylamine. Analogous protonation and methylation reactions have been observed with the tellurium complex (μ-Te)(η5-C5H5)Cr(CO)3]2 (3); the ionic compounds (μ-TeH)(η5-C5H5)Cr(CO)32]BF4 (4a) and (μ-TeCH3) (η5-C5H5)Cr(CO)32]PF6(4a), respectively, are obtained. In contrast, the electron-deficient tellurium ligand of the manganese complex (μ3-Te)(η5-C5H5)Mn(CO)2]3 (5) is neither attacked by Brønsted acids nor by electrophilic methylating agents (e.g., CF3SO3CH3) but is rather methylated by methyllithium to give the anionic species (μ3-TeCH3)η5-C5H5)Mn(CO)23]? that can be isolated pure as the PPN+ salt 6. |
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| Keywords: | To whom correspondence should be addressed |
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