Electrosynthesis of nickel phosphides on the basis of white phosphorus

Budnikova, Yu. G.; Tazeev, D. I.; Трофимов, Б. А.; Sinyashin, Оleg G.

doi:10.1016/j.elecom.2004.05.007

Cited by 20 publications

(14 citation statements)

References 10 publications

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“…16 Similar results are observed in the case of the electro chemical reduction of the nickel complexes with phen and PPh 3 in the presence of white phosphorus.…”

Section: Complexsupporting

confidence: 82%

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

et al. 2005

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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 P 4 molecule with the metal, resulting in the deformation of the P 4 tetrahedron without destruction. This case is characteristic of the NiX 2 L complexes, which are reduced at higher cathodic potentials (|E red | > 0.9 V) (X = BF 4 , Br, and Cl; L is bpy in DMF, MeCN, and acetone; 2,9 dimethyl 1,10 phenanthroline (phen) and PPh 3 in DMF and acetone). To cleave the P-P bonds in the P 4 molecule, this complex should be reduced on the electrode. The second route is the oxidation of white phosphorus in the coordination sphere of the Ni II complex. It occurs when the complex has a sufficiently high oxidizing ability and is reduced rather easily (|E red | < 0.9 V) (X = BF 4 , 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) (n 2 p 2 ) in DMF; phen and PPh 3 in MeCN). The P 4 molecule opening is observed to form a new Ni I complex containing the (P 3 ) fragment, for example, [(triphos)Ni(P 3 )Ni(triphos)](BF 4 ) 2 .The electrochemical activation of reagents in processes involving organometallic compounds is very efficient. 1-4 This approach combines advantages of catalysis by metal complexes and activation by means of electrochemical electron transfer. The activation of white phosphorus is a practically important task because of the necessity to search for new routes of direct syntheses of organophos phorus compounds. Numerous reactions of P 4 tetrahedron transformation were described, which resulted in various polyphosphorus structures among which metal complexes with cyclic P 3 , P 5 , and P 6 ligands, 4 as well as the P 4 ligand, 5,6 seem to be most interesting. The P 4 molecule is activated due to the deformation of the P 4 tetrahedron and, as a consequence, the P-P bond length changes. In ultimate cases, these bonds can cleave to form new polyphosphorus structures. Until now, P 4 transformation was studied only by NMR spectroscopy, and very stable compounds were examined. Evidently, the more stable these structures, the more difficult is the preparation of related basis organophosphorus compounds, i.e., the main task of the elemental phosphorus chemistry is the direct transformation of phosphorus into organophosphorus compounds (OPC), excluding traditional steps of its chlo rination. At the same time, metal complexes with poly phosphorus ligands can possess a set of useful properties: semiconductivity, corrosion resistance, and others 7 and act as stable intermediates in various reactions, which are of independent interest.In this work, we attempted to estimate the reactivity of several nickel complexes with σ donor ligands toward white phosphorus using cyclic voltammetry (CV), pre parative electrolysis, and 31 P NMR spectroscopy. The nickel complexes were chosen, because they are catalysts of some reactions of white phosphorus functio...

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“…16 Similar results are observed in the case of the electro chemical reduction of the nickel complexes with phen and PPh 3 in the presence of white phosphorus.…”

Section: Complexsupporting

confidence: 82%

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

et al. 2005

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“…In the case of nickel anode, a dark precipitate formed, which seems to be insoluble nickel phosphides as in the case of the recently described electro chemical preparation of these compounds from white phosphorus. 25 Thus, the studies performed and the experimental results allow conclusion that electrochemical reduction of elemental (white) phosphorus in the undivided cell equipped with electrochemically soluble Al, Co, Nb, and Sn anodes results in the formation of P 4 2-dianion as the reduction intermediate. The efficiency of elec trochemical preparation of P 4 2-can be increased us ing organic mediators capable of homogeneous reduc tion of white phosphorus in the bulk solution.…”

Section: Resultsmentioning

confidence: 95%

Electrochemical generation of P4 2– dianion from white phosphorus

et al. 2014

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“…The electrochemical reduction of white phosphorus was not studied in details up to now, the mechanism of its activation and transformation with P-P bond cleavage under electron transfer on electrodes of the various nature was not clear. The data on potentials of Р 4 reduction on glassy carbon and mercury were published earlier [23], the ways of transformation of white phosphorus under the complexes of nickel, including generated electrochemically were described [29][30][31].…”

Section: Cva Of White Phosphorusmentioning

confidence: 99%