Polynuclear Iron and Rhodium Complexes of 7-Oxahericene (2,3,5,6-Tetramethylidenebicycloheptan-7-one

Article abstract of DOI:10.1002/hlca.19890720121

μ-Carbonyl(Rh - Rh)di(η⁵-indenyl)<(2R,3S)-C,2,3,C-η-(2,3,4,5-tetramethylidenebicyclo<2.2.1>heptan-7-one)>-dirhodium(I)(Rh-Rh) (7) and cis-μ-<(2R,3S,5R,6S)-C,2,3,C-η:C,5,6,C-η-(2,3,5,6-tetramethylidenebicyclo<2.2.1>heptan-7-one)>bis<μ-carbonyldi(η⁵-indenyl)dirhodium(I)(Rh-Rh)> (8) have been prepared.Complex 7 reacts with Fe2(CO)9 in hexane/MeOH and gives cis-μ-<(2R,3S,5R,6S)-> (9), trans-μ-<(2R,3S,5S,6R)-C,2,3-η: C,5,6,C-η-(2,3,5,6,tetramethylidenebicyclo<2.2.1>heptan-7-one)>-μ-carbonyldi(η⁵-indenyl)dirhodium(I)(Rh-Rh)-(tricarbonyliron) (10), and μ-carbonyl(Rh-Rh)<(2R,3S)-C,2,3,C-η-(2,3-dimethyl-5,6-dimethylidenebicyclo<2.2.1>hept-2-en-7-one)>di(η⁵-indenyl)dirhodium(I)Rh-Rh) (11).Treatment of 7-oxa<2.2.1>hericene (4) with Fe2(CO)9 or (cyclooctene)2Fe(CO)3 gave a 1 : 2 mixture of cis-μ-<(2R,3S,5R,6S)-> (12) and trans-μ-<(2R,3S,5S,6R)-C,2,3,C-η:C,5,6,C-η-(2,3,5,6-tetramethylidenebicyclo<2.2.1>heptan-7-one)>bis(tricarbonyliron) (13).