In this work, [MX2(R2PCH2)(2)NMe] complexes have been modeled and studied by density functional theory (DFT). The metal M (M = Ni. Pt, Pd), the halogen X (X = Cl, Br, I) and the substituent R (R = Me. Cy, Ph) on the phosphorus atoms were systematically combined to 27 different complexes. Replacing the nitrogen atom on the ligind with a methylene group and the methyl group on the nitrogen atom with a phenyl group were two additional variations considered in this work. Electronic and structural properties of each complex were examined and general trends were derived. Pd-P bond lengths were found to be longer than Pt-P bond lengths reflecting the well-known Lanthanide contraction. The modification of the amino part turned out to be most sensitive with regard to changes in the geometry and the electronic structure of the complexes. Therefore, it may serve as a sensitive tool for the design and synthesis of new catalysts as well as antibiotics based on aminomethylphosphine complexes. (C) 2008 Elsevier B.V. All rights reserved.