INDO SCF molecular orbital calculations for π-cyclopentadienyl-π-cyclopropenylnickel indicate a formally d 10 configuration for the metal. Calculations of the ionisation energies show that electron loss should take place first from the occupied closely grouped set of dominantly d-orbitals, and then from a mainly π-cyclopentadienyl e orbital, this being the highest occupied ligand level. This latter level shows however only a slight mixing with the metal d-orbitals, resulting in a small ligand→metal electron donation; the dominant interaction is that between the higher lying π-cyclopropenyl e level and the metal 3 d xz and 3 d yz orbitals which leads to a substantial metal→ligand charge donation. The behaviour of the π-cyclopropenyl ligand is discussed using the calculated charge distributions.