Mononuclear cobalt(0) complexes containing diolefin and trimethylphosphane ligands Co(cycloocta-1,5-diene)(PMe3)2 and Co[(CH2=CHMe2Si)2O](PMe3)2 are obtained from CoCl2 by reaction with magnesium in the presence of the ligands or by substitution of cobalt(olefin)tris- (trimethylphosphane) with diolefin. Chemical and spectroscopic properties confirm the para- magnetic valence state of the compounds in solution. An X-Ray crystal structure determination of Co[(CH2=CHMe2Si)2O](PMe3)2 shows a tetrahedral arrangement of ligand functions around the cobalt atom. With butadiene a diamagnetic dinuclear complex [Co(C4H6)(PMe3)3]2 is obtained containing π-allyl co-ordination of two Co(PMe3)3 units to a linear dimer of butadiene