GEHINDERTE LIGANDBEWEGUNGEN IN UEBERGANGSMETALLKOMPLEXEN XXIX. PHOTOREAKTION VON Mn2(CO)10 MIT 1,1-DIMETHYLALLEN: ENYLKOMOLEXE MIT C-H-Mn-BRUECKEN

Article abstract of DOI:10.1016/0022-328X(86)80085-7

Decacarbonyldimanganese(O) (I) gives photochemically with 1,1-dimethylallene (II) at 248 K a mixture of three mononuclear and two dinuclear complexes, which are separated by HPLC.The main product of the reaction is the bridged octacarbonyl μ-η^2:2-1,1-dimethylallene-dimanganese(O) (V).As side products, a mixture of the isomeric tetracarbonyl-η³-methyl-2-buten-1-yl-manganese (III) and tetracarbonyl-η³-2-methyl-2-buten-1-yl-manganese (IV) is obtained.In addition the novel electron deficient compounds tricarbonyl-η^3:CH-2-methyl-E-3-(3(8), 6-m-menthadien-6-yl)-2-buten-1-yl-manganese (VI) and hexacarbonyl-μ-η^3:CH:3:CH-2,3,4,5-tetramethyl-2,5-hexadien-1,4-diyl-dimanganese (VII) are isolated.VI and VII add under ambient conditions reversibly carbon monoxide and form the moderately stable tetracarbonyl-η³-2-methyl-E-3-(3(8), 6-m-menthadien-6-yl)-2-buten-1-yl-manganese (VIII) and the instable hepta- and octacarbonyl-μ-η^3:3-2,3,4,5-tetramethyl-2,5-hexadien-1,4-diyl-dimanganese (IX,X).The mixture of the isomers III and IV, and the complexes V-VIII were characterized by C and H elemental analyses and by NMR and IR spectroscopy.The molecular structures of VI and VII were determined by X-ray structure analyses.