Phosphinohydrazines and phosphinohydrazides M(–N(R)–N(R)–PPh2)n of some transition and main group metals: synthesis and characterization

The rearrangement of phosphitohydrazide ligand [(ArO)2P–NPh–NPh–] into iminophosphoranate anion [(PhNP(OAr)2–NPh–] {(ArO)2P = [CH2(tBuMeC6H2O)2P]} in coordination sphere of divalent cobalt

“…The P(1)-N(1) and N(1)-N(2) bond lengths in the molecule (1.698(2) and 1.420(3) Å, respectively) are typical for phosphazanes and phosphinohydrazines [2,5]. Note, however, the N-N bond distance in 2 is somewhat longer than that found in monophosphinohydrazine analog PhNH-NPh-PPh 2 (1.401(2)) [1]. Eight-membered heterocycle in 2 demonstrates chair-like conformation.…”

“…Recently it was shown that rearrangements of mono-, bisand tris(diphenylphosphino)hydrazide ligands, Ph 2 P-NPh-NPh-, (Ph 2 P) 2 N-NPh-, (Ph 2 P) 2 N-N(PPh 2 )-, in the coordination sphere of nickel(II), cobalt(II) and iron(III) result in the formation of metal complexes of the phosphazene and phosphinoamide type depending on the starting ligand [1][2][3] (see Scheme 1).…”

Transformations of phosphazane ligands in the coordination sphere of transition metals. Reactions of phosphinotriazene Ph2P-N(Ph)-N=NPh with Ni0 and NiI complexes

“…12 In the radi cal anion of DFTA, the N-N bond is substantially elon gated (1.41(1) Å). 12 In the crystal, the anions of (DFTA) 3 Ni form pseudo dimers through weak intermolecular interactions between the central N(5) atom of the triazenide fragment and the H(28) atom of the phenyl ring. The N...H intermolecular distances are 2.568(7) Å, which is slightly smaller than the average length of the normal van der Waals contact for these atoms (2.64 Å).…”

“…1,2 Since the nitrogen and phosphorus atoms are prone to coordinate to metals, various mo lecular rearrangements and transformations of the phosphazane ligands can occur in the coordination sphere of transition metals. Earlier, 3 we have studied ther mal transformations of the phosphinohydrazine ligands {-NAr-NAr-PPh 2 (Ar = Ph, 4 Bu t C 6 H 4 )} in the coor dination sphere of transition metals. In particular, it has been demonstrated that reactions of the phosphino hydrazine ligand with Co 2+ , Ni 2+ , or Fe 3+ complexes result in isomerization of the former to the amino iminophosphorane ligand {-NPh-PPh 2 =NPh} giv ing rise to the corresponding metal complexes M[NPh-PPh 2 =NPh] n in quantitative yields (Scheme 1).…”

“…Molecular structure of [Ph 4 P] + [Ni(PhNNNPh)3 ] -(4). The hydrogen atoms and toluene solvate molecules are omitted.…”