From a 44-electron to a 48-electron trinuclear phosphido platinum complex: density functional study of [{(CF3)(PH3)Pt(μ-PH2)(μ-H)}2Pt] and [{(CF3)(PH3)Pt(μ-PH2)(μ-I)}2Pt] model compounds

Treatment of [{(C6F5)(PPh3)Pt(μ-PPh2)(μ-H)}2Pt] (1) with I2 results in a complicated reaction from which [{(C6F5)(PPh3)Pt(μ-PPh2)(μ-I)}2Pt] (2) is obtained. The X-ray structure and 19F and 31P NMR spectra are given. Density functional theory (DFT) at the B3LYP level, using the LANL2DZ basis set, provides a satisfactory description of structural, bonding, electronic and related properties of [{(CF3)(PH3)Pt(μ-PH2)(μ-H)}2Pt] and [{(CF3)(PH3)Pt(μ-PH2)(μ-I)}2Pt] model compounds. The results unambiguously justify the predictions of the through-ring bonding required by the number of framework electrons and threw light on the bonding mechanism in the “{Pt(μ-X)(μ-PH2)}2Pt” (X=H, I) nuclear framework of the compounds.