OPTICALLY-ACTIVE TRANSITION-METAL COMPLEXES .1. IRON, COBALT AND RHODIUM COMPLEXES OF THE OPTICALLY-ACTIVE DIOLEFIN (+)-NOPADIENE AND ITS DERIVATIVES - THE CRYSTAL-STRUCTURE OF C5ME5RH(NOPADIENE)

The syntheses of metal complexes of the optically active diolefins nopadiene, acetylnopadiene, nopadiene acid and nopadiene aldehyde are described. All the ligands were coordinated to the Fe(CO)3 group and some also to CpRh, CpCo, Cp*Rh and Cp*Co (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl). The complexation was disatereoselective in most cases and optically active diolefin compounds were directly obtained. The solid state structure of one isomer of C5Me5Rh(nopadiene) is described. Various chemical transformations, such as reductions and nucleophilic additions at functional groups, are reported; depending on reaction type, these proceed diastereoselectively or even enantioselectively with generation of new chiral carbon centers. In these reactions, pronounced differences are observed in the reactivity and selectivity of complexed and free ligands. Efficient substitutions of carbonyl groups for phosphines and phosphites are also described for (nopadiene)Fe(CO)3.