Highly reactive σ-organonickel complexes in electrocatalytic processes

Electrocatalytic eco-efficient functionalization of white phosphorus

“…Under favorable conditions single bonds of a tetraphosphorus molecule could also be involved in the above reaction and new effective way of selective electrosynthesis of compounds with P-C bonds from white phosphorus in mild conditions of metal complex catalysis was elaborated. We supposed that white phosphorus can be involved to the reaction with alkyl and aryl halides under conditions of cyclic regeneration of metallocomplex catalyst at the electrode [23][24][25][26][27]30].…”

“…By analogy with the white phosphorus functionalization process by Grignard reagents, it is proposed that a key stage of the reaction consists in the interaction of organonickel compound, [RNi II XL n ], with white phosphorus according to the following scheme [23][24][25][26][27]30]:…”

Reactions of Elemental Phosphorus with Electrophiles in Super Basic Systems: XVII. Phosphorylation of Arylalkenes with Active Modifications of Elemental Phosphorus

“…There has been devised and developed a new method of activation of elemental phosphorus (including its the least active red modification) in heterogenous super basic systems, that opens up the way to formation of a C3P bond and allows preparation of previously unknown or hardly available phosphines and phosphine oxides, including unsaturated, chiral, and polyfunctional [1,4,5,739]. To facilitate P3P bond cleavage in the P 4 molecule and thus enhance its reactivity, introduction of white phosphorus in the coordination sphere of the transition metal with subsequent (or preceding) electrochemical electron transfer [6], as well as activation and functionalization of white phosphorus on Rh [2] have been used to success.…”

First Example of Microwave Activation of Elementary Phosphorus in the Reaction with 2-Vinylpyridine

“…For the facilitation of the cleavage of P3P bonds in the molecule of elemental phosphorus and hence for the increase of its reactivity special reagents and catalytic systems (for example heterogenic highly basic media [1, 2, 4]) as well as the introduction of white phosphorus in the coordinational sphere of the transition metal [3,5]) and also the methods of external action on the macromolecule of red phosphorus (X-ray ir-ÄÄÄÄÄÄÄÄÄÄÄÄ radiation, mechanochemical or ultrasound treatment [6,7]) are successfully used.In the present work on an example of direct phosphorylation of 2-vinylpyridine with red phosphorus it was for the first time shown that microwave activation of the latter in the synthesis of organophosphorus compounds is possible. Hence, microwave irradiation of reagents for 2 min in KOH3DMSO system permits to obtain tris[2-(2-pyridyl)-ethyl]-(I) and bis[2-(2-pyridyl)ethyl]phosphine oxide (II) (yield 48% and 12% respectively), the effective polydentate ligands and building blocks [8].…”

“…For the facilitation of the cleavage of P3P bonds in the molecule of elemental phosphorus and hence for the increase of its reactivity special reagents and catalytic systems (for example heterogenic highly basic media [1,2,4]) as well as the introduction of white phosphorus in the coordinational sphere of the transition metal [3,5]) and also the methods of external action on the macromolecule of red phosphorus (X-ray ir-ÄÄÄÄÄÄÄÄÄÄÄÄ radiation, mechanochemical or ultrasound treatment [6,7]) are successfully used.…”