17985-98-7Relevant articles and documents
Phosphinohydrazines and phosphinohydrazides M(-N(R)-N(R) -PPh2)n of some transition and main group metals: Synthesis and characterization. Rearrangement of Ph2 P-NR-NR- ligands into aminoiminophosphorane, RN=PPh2-NR-, and related chemistry
Fedotova, Yana V.,Kornev, Alexander N.,Sushev, Vyacheslav V.,Kursky, Yurii A.,Mushtina, Tatiana G.,Makarenko, Natalia P.,Fukin, Georgy K.,Abakumov, Gleb A.,Zakharov, Lev N.,Rheingold, Arnold L.
, p. 3060 - 3074 (2007/10/03)
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) ?. 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-PPh2NAr) n. Complex Co[N(C6H4But) -PPh2 = N-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(PhN = NPh), while copper(I) silylamide originally forms (PhNH-NPh-PPh2)2 CuN(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-PPh2NPh]· 2HCl (3) in quantitative yield.
