Activation of white phosphorus in the coordination sphere of nickel complexes with σ-donor ligands

Autor: Dmitry G. Yakhvarov, D. I. Tazeev, A. G. Kafiyatullina, Nina K. Gusarova, Vladimir I. Morozov, Oleg G. Sinyashin, Yu. G. Budnikova, Boris A. Trofimov
Rok vydání: 2005
Předmět:
Zdroj: Russian Chemical Bulletin. 54:942-947
ISSN: 1573-9171
1066-5285
Popis: Routes of white phosphorus activation in the coordination sphere of the nickel complexes with different ligands are shown. The first route is based on the coordination of a P4 molecule with the metal, resulting in the deformation of the P4 tetrahedron without destruction. This case is characteristic of the NiX2L complexes, which are reduced at higher cathodic potentials (|Ered| > 0.9 V) (X = BF4, Br, and Cl; L is bpy in DMF, MeCN, and acetone; 2,9-dimethyl-1,10-phenanthroline (phen) and PPh3 in DMF and acetone). To cleave the P—P bonds in the P4 molecule, this complex should be reduced on the electrode. The second route is the oxidation of white phosphorus in the coordination sphere of the NiII complex. It occurs when the complex has a sufficiently high oxidizing ability and is reduced rather easily (|Ered| < 0.9 V) (X = BF4, L is 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) in acetone; 1,1′,5,5′-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (n2p2) in DMF; phen and PPh3 in MeCN). The P4 molecule opening is observed to form a new NiI complex containing the (P3) fragment, for example, [(triphos)Ni(P3)Ni(triphos)](BF4)2.
Databáze: OpenAIRE
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