PHOTOCHEMISCHE REAKTIONEN VON UEBERGANGSMETALL-ORGANYL-KOMPLEXEN MIT OLEFINEN. II. DIE UMSETZUNG VON PENTACARBONYL-PHENYL-MANGAN MIT 6,6-DIMETHYL- UND 6,6-DIPHENYLFULVEN

Article abstract of DOI:10.1016/S0022-328X(00)99229-5

C6H5Mn(CO)5 (I) reacts photochemically with 6,6-dimethyl- or 6,6-diphenylfulvene (II, III) to labile C6H5(CO)4Mn(η²-fulvene) complexes.These rearrange thermally by insertion of the two ring double bonds of the fulvenes into the Mn-C6H5 bond to 1,2- and 1,3-substituted (CO)4Mn(η-3-cyclopenten-5-yl) complexes (IV-VII) which were separated by HPLC.The formation of the 1,3-substituted isomers V and VII is accompanied by a 1,5-H shift.V and VII readily loose one CO at room temperature and further rearrange to 1,3-disubstituted (CO)3Mn(η-cyclopentadienyl) (VIII, IX).The latter are also formed by thermal reactions of I with II, or III, respectively.The structures of the isolated complexes IV-IX were elucidated by IR, 1H NMR and mass spectroscopy.