The stereochemistry of cleavage of some alkenylmanganese carbonyl derivatives |
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| Affiliation: | 1. Department of Chemistry, University of Otago, Union Place West, Dunedin 9054, New Zealand;2. Centre for Trace Element Analysis, University of Otago, Union Place West, Dunedin 9054, New Zealand;3. Jacobs University Bremen, Department of Physics and Earth Sciences, Campus Ring 1, 28759 Bremen, Germany;4. NIWA/University of Otago Research Centre for Oceanography, University of Otago, Union Place West, Dunedin 9054, New Zealand;5. Antarctic Climate & Ecosystems Cooperative Research Centre (ACE CRC), University of Tasmania, 20 Castray Esplanade, Hobart 7000, Australia;6. Marine Environmental Studies Laboratory, Division of IAEA Environment Laboratories, Department of Nuclear Sciences and Applications, International Atomic Energy Agency, Monaco, Principality of Monaco |
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| Abstract: | Cleavage of the compounds trans-RCHCRMn(CO)5 (where R = CF3, CO2Me or CO2H) with HMn(CO)5 occurs with complete retention of configuration to yield the corresponding trans-olefins and Mn2(CO)10. Reaction of the cmpound where R = CF3 with bromine occurs similarly with retention of configuration to give trans-CF3CHC(CF3)Br, whereas cleavage of the compound where R = CO2H with bromine proceeds with complete inversion of configuration. The compounds cis-MeO2CCHlCH7z.sbnd;Mn(CO)5 and trans-MeO2CCHC(CO2Me)Mn(CO)5 react with bromine to give mixtures of cis- and trans-MeO2CCHCHBr (ratio cis/trans 3/7), and cis- and trans-MeO2CCHCBrCO2Me (ratio cis/trans 7/3) respectively.Hydridopentacarbonylmanganese has also been shown to react with MeC2Me or EtC2Et to give mainly cis-2-butene and cis-3-hexene respectively, probably by a cis hydride addition followed by stereospecific hydride cleavage. Diphenylacetylene under similar conditions gives trans-stilbene, but as rapid cis/trans isomerisation has also been shown to occur under these conditions, no conclusions regarding the sterochemistry of the hydride addition step could be reached. |
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