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 ((Me 2 P) 2 NN(Me)(PMe 2 ))

The new triphosphine (Me 2 P) 2 NN(Me)(PMe 2 ) ( 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 (>PN(R)P<) and phosphanyl hydrazide (>PN(R)N(R)P<) backbones. Reaction of 1 with cis ‐[W(CO) 4 (NHC 5 H 10 ) 2 ] proceeds via two coordination modes to give four‐membered MPNP and five‐membered MPNNP metallacyclic frameworks. The tungsten complex cis ‐[W(CO) 4 {(Me 2 P) 2 NN(Me)(PMe 2 )}] ( 2 ) possessing an uncoordinated phosphine moiety to prepare multimetallic organometallic compounds. For example, reactions of 2 with PdCl 2 (PhCN) 2 and PtCl 2 (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 31 P NMR spectroscopy.