Inorganic Chemistry, Vol.38, No.2, 340-345, 1999
Electron counting scheme relevant for late transition metal compounds with weakly electronegative ligands. Electronic band structure study of phosphosilicides PtSi3P2 and NiSi2P3
The conventional electron counting scheme often leads to erroneous predictions for late transition metal compounds with weakly electronegative main group ligand atoms. The cause for this deficiency was analyzed, and a modified electron counting scheme was proposed for predicting the frontier orbitals of such compounds. The modified scheme predicts that the transition metal atoms of such compounds have a d(10) electron count, and their frontier orbitals are represented by the highest-lying lone pair levels of the main group ligand atoms. These predictions were tested by carrying, out electronic band structure calculations for phosphosilicides PtSi3P2 and NiSi2P3. The relevance of nonstoichiometric compositions of these phases was also discussed.