Phosphinohydrazines and phosphinohydrazides M(–N(R)–N(R)–PPh2)n of some transition and main group metals: synthesis and characterization: Rearrangement of Ph2P–NR–NR– ligands into aminoiminophosphorane, RNdouble bond; length as m-dashPPh2–NR–, and related

The reactions of phosphinohydrazines ArNH–N(Ar)–PPh2 {Ar = Ph (2a), p-But–C6H4– (2b)} with metal silylamides M[N(SiMe3)2]n, {M = Fe(II), Fe(III), Co(II), Ni(I), Cu(I)} or the reactions of lithium salts ArN(Li)–N(Ar)–PPh2 with metal halides (GeCl2, ZnCl2, FeBr2, CoCl2, NiBr2, CrCl3, MnCl2) are strongly dependent on nature of a metal and its ligand environment.Early transition metals or non-transition metals form stable phosphinohydrazides M[N(Ar)N(Ar)PPh2]n {M = Li, Zn, Ge(II), Mn(II), Cr(III), Fe(II)}.Starting ligand 2a and germylene Ge(NPhNPhPPh2)2 (7) were characterized by X-ray analysis.Germanium is coordinated additionally with a phosphorus atom of one of the diphenylphosphine groups.The distance Ge⋯P was found to be 2.563(1) Å.This coordination leads to an appreciable increase in a pyramidal geometry of nitrogen atoms relatively to a non-coordinated fragment.Late transition metals (Co, Ni, Cu) and metals with enhanced oxidation state (Fe3+) cause transformation of a phosphinohydrazide ligand.For Co(II), Ni(II), Fe(III) this leads quantitatively to aminoiminophosphoranates M(NAr–PPh2double bond; length as m-dashNAr)n.Complex Co[N(C6H4But)–PPh2double bond; length as m-dashN–C6H4But]2 (11) was characterized by X-ray analysis.Nickel(I) silylamide, (Ph3P)2NiN(SiMe3)2, being reacted with 2a yields azobenzene complex, (Ph3P)2Ni(PhNdouble bond; length as m-dashNPh), while copper(I) silylamide originally forms (PhNH–NPh–PPh2)2CuN(SiMe3)2 (18).Heating of the latter in toluene solution yields insoluble copper(I) diphenylphosphide, azobenzene, 2a and hexamethyldisilazane.The reaction of hydrazobenzene with Ph2PCl (1:1) in methylene chloride for three days gives aminoiminophosphorane dihydrochloride[PhNH–PPh2double bond; length as m-dashNPh] · 2HCl (3) in quantitative yield.