Migratory insertion of the R2P group into a nitrogen-nitrogen bond - a novel type of rearrangement in phosphorus-nitrogen ligand chemistry. 3. The rearrangement of triphosphinohydrazide ligand -N(PPh2)-N(PPh2)2 to triphosphazenide anion {[(Ph2P-N]2PPh2}- in the coordination sphere of divalent cobalt and nickel

Vyacheslav V Sushev; Natalia V Belina; Georgy K Fukin; Yuriy A Kurskiy; Alexander N Kornev; Gleb A Abakumov

doi:10.1021/ic701954k

Migratory insertion of the R2P group into a nitrogen-nitrogen bond - a novel type of rearrangement in phosphorus-nitrogen ligand chemistry. 3. The rearrangement of triphosphinohydrazide ligand -N(PPh2)-N(PPh2)2 to triphosphazenide anion {[(Ph2P-N]2PPh2}- in the coordination sphere of divalent cobalt and nickel

Inorg Chem. 2008 Apr 7;47(7):2608-12. doi: 10.1021/ic701954k. Epub 2008 Mar 4.

Authors

Vyacheslav V Sushev¹, Natalia V Belina, Georgy K Fukin, Yuriy A Kurskiy, Alexander N Kornev, Gleb A Abakumov

Affiliation

¹ Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Street, 603950 Nizhny Novgorod, Russia.

PMID: 18318475
DOI: 10.1021/ic701954k

Abstract

Hydrazine dihydrochloride reacts with 3 equiv of Ph2PCl in tetrahydrofuran in the presence of triethylamine to give tris(diphenylphosphino)hydrazine (1) in 70% yield. Each nitrogen atom in 1 has a trigonal-planar environment according to X-ray analysis. Thermolysis of 1 at 130 degrees C results in the formation of two products: bis(diphenylphosphino)amine and octaphenylcyclotetraphosphazene. The interaction of free ligand 1 with NiBr2 affords a simple adduct [(Ph2P)2N-NH-PPh2]NiBr2, while its anionic (hydrazide) form undergoes rearrangement in a coordination sphere of divalent cobalt and nickel involving migratory insertion of the Ph2P group into a nitrogen-nitrogen bond. The reaction of 1 with cobalt bis(trimethylsilyl)amide, [(Me3Si)2N]2Co, yields the complex of phosphazenide-type (Me3Si)2N-Co[(Ph2PN)2PPh2] (2) in 86% yield. A similar reaction of 1 with nikelocene proceeds with substitution of one Cp ring to form durable 18-electron complex CpNi[(Ph2PN)2PPh2] (3).