The complexes C5H5Co(PMe3)2 (1), C9H7Co(PMe3)2 (2) and (C5H4CF3)Co(PMe3)2 (3) react with mono- and disubstituted ethenes such as styrene, acrylic acid methylester, methylvinylketone, acroleine, acrylic acid amide, acrylonitrile, maleic anhydride, maleic and fumaric acid dimethylester, and fumaric dinitrile to give the olefin(phosphane)cobalt compounds (ring)Co(PMe3)(olefin) (4-32) in good to excellent yields. With acrylonitrile, two different rotamers are obtained which indicates that there is a considerable energy barrier for rotation around the metal-olefin bond. The reactions of 1 and 3 with maleic acid dimethylester (MDE) lead not only to the formation of the expected products (ring)Co(PMe3)(MDE) (22, 23) but also to the thermodynamically favored isomers (ring)Co(PMe3)(FDE) (24, 26) containing fumaric acid dimethylester (FDE) as ligand. A similar isomerization has been observed upon treatment of 2 and 3 with fumaric dinitrile (FDN) which gives besides the complexes (ring)Co(PMe3)(FDN) (29, 31) also the maleic dinitrile (MDN) derivatives (ring)Co(PMe3)(MDN) (30, 32). The olefin(trimethylphosphane)cobalt compounds are surprisingly inert and neither on photolysis nor on heating give the isomeric hydrido(vinyl)metal complexes.
Cis-trans Isomerase Isomerisation from Maleic Acid to Fumaric Acid
