The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes

The reactivities of phosphanylphosphinidene complexes [(DippN)₂W(Cl)(η²-P-PtBu₂)]^- (1), [(pTol₃P)₂Pt(η²-P═PtBu₂)] (2), and [(dppe)Pt(η²-P═PtBu₂)] (3) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex (1) with stochiometric Br(CH₂)Br (n = 3, 4, 6) led to the formation of neutral complexes with a tBu₂PP(CH₂)₃Br ligand or neutral dinuclear complexes with unusual tetradentate tBu₂PP(CH₂)_nPPtBu₂ ligands (n = 4, 6). The methylation of platinum complexes 2 and 3 with MeI yielded neutral or cationic complexes bearing side-on coordinated tBu₂P-P-Me moieties. The reaction of 2 with I(CH₂)₂I gave a platinum complex with a tBu₂P-P-I ligand. When the same dihaloalkane was reacted with 3, the P-P bond in the phosphanylphosphinidene ligand was cleaved to yield tBu₂PI, phosphorus polymers, [(dppe)PtI₂] and C₂H₄. Furthermore, the reaction of 3 with Br(CH₂)₂Br yielded dinuclear complex bearing a tetraphosphorus tBu₂PPPPtBu₂ ligand in the coordination sphere of the platinum. The molecular structures of the isolated products were established in the solid state and in solution by single-crystal X-ray diffraction and NMR spectroscopy. DFT studies indicated that the polyphosphorus ligands in the obtained complexes possess structures similar to free phosphenium cations tBu₂P⁺═P-R (R = Me, I) or (tBu₂P⁺═P)₂.