Photochemie fulvalenverbrückter metallcarbonyl-komplexe: Das beispiel hexacarbonyl-(μ,η55-fulvalen)dimangan

Wolfgang A. Herrmann, Dirk Andrejewski, Eberhardt Herdtweck

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Photolysis of hexacarbonyl(μ,η5: η5-fulvalene)dimanganese (2) in benzene in the presence of π-donor ligands gives monosubstituted derivatives of composition (μ,η5: η5-C10H8)Mn2(CO)5L (4c-e; L = ethylene, cyclooctene, and 2-butyne) while σ-donor ligands yields disubstituted complexes (μ, η5: η5-C10H8)Mn2(CO)4L2 (3a, 5a,b,f; L = THF, P(C6H5)3, (C6H5)2PCH2P(C6H5)2, C5H5N), The π-donor ligand diphenylacetylene (5g) is an exception as it also entails disubstitution at 2 upon photolysis. The bridged, dinuclear complex 5b has been characterized by means of a single-crystal X-ray study: the fulvalene bridging ligand exhibits a rather twisted conformation (interplanar angle 65.4°); this very pronounced twisting effect and the (non-bonding) manganese-manganese distance of 458.8 pm are generated by the rigid diphosphane chelating ligands.

Original languageGerman
Pages (from-to)183-195
Number of pages13
JournalJournal of Organometallic Chemistry
Issue number2
StatePublished - 13 Jan 1987

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