Transition Metal Chemistry of Main Group Hydrazides. 17. Triphosphine derived from phosphanyl hydrazide as a building block for hetero trimetallic compounds. Synthesis and coordination chemistry of ((Me2P)2N?N(Me)(PMe2))

The new triphosphine (Me₂P)₂N? N(Me)(PMe₂) ( 1 ), has been synthesized in pure form by the reaction of methylhydrazine with dimethylchlorophosphine in the presence of triethylamine. This triphosphine represents a bridge between phosphinoamine (>P? N(R)? P<) and phosphanyl hydrazide (>P? N(R)? N(R)? P<) backbones. Reaction of 1 with cis-W(CO)₄(NHC₅H₁₀)₂] proceeds via two coordination modes to give four-membered M? P? N? P and five-membered M? P? N? N? P metallacyclic frameworks. The tungsten complex cis-W(CO)₄{(Me₂P)₂NN(Me)(PMe₂)}] ( 2 ) possessing an uncoordinated phosphine moiety to prepare multimetallic organometallic compounds. For example, reactions of 2 with PdCl₂(PhCN)₂ and PtCl₂(COD) produced the trimetallic complexes consisting of W(0)? Pt(II) and W(0)? Pd(II) centers respectively in good yields. The different isomers of these trinuclear complexes have been clearly identified by ³¹P NMR spectroscopy.