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Budnikova, Yu. G.; Yakhvarov, Dmitry G.; Морозов, В. И.; Kargin, Yu. M.; Il'yasov, A. V.; Vyakhireva, Yu. N.; Sinyashin, Оleg G.

doi:10.1023/a:1015401029839

Cited by 25 publications

(21 citation statements)

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“…(2)). The data obtained by ESR spectroscopy (g = 2.007) 16 show that in this particle the electron is predominantly local ized on the ligand. As a whole, the electrochemical be havior of this complex is similar to that of the earlier described 16 [NiBr 2 (bpy)] complex under similar electro chemical conditions.…”

Section: Resultsmentioning

confidence: 88%

Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

et al. 2007

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The reduction of aryldichlorophosphines in organic solvents was studied by cyclic voltammetry, preparative electrolysis, and chemical reduction. The reaction of the electro chemically generated (2,2´ bipyridine)nickel(0) complexes with aryldichlorophosphines PhPCl 2 and tippPCl 2 (tipp is 2,4,6 triisopropylphenyl) proceeds through the formation of highly reac tive organophosphorus intermediates, whose reactions with diphenylacetylene and hex 1 ene afford phosphirene and phosphirane heterocycles, respectively.The search for new highly efficient synthetic methods is one of the principal trends of the chemistry of organo metallic and organophosphorus compounds. 1 The forma tion of element-carbon bonds, especially phospho rus-carbon bond, is an important goal of the modern organoelement chemistry. 2,3 In this context, special at tention is given to the development of novel approaches to the target synthesis of chemical compounds from highly reactive organophosphorus intermediates. Examples of such intermediates are derivatives of low coordinate phos phorus, viz., phosphinidenes [RP:] (phosphorus analogs of carbenes), which play a significant role in the synthesis of earlier unknown organophosphorus and heterocyclic compounds. 3-5 In preparative synthesis these short lived species are used, as a rule, as transition metal complexes. Presently the main and most appropriate method for their generation is the thermal decomposition of the corre sponding tungsten and molybdenum 7 phosphanorborna diene complexes. 6 Many publications are focused to the direct synthesis of various stable metal phosphinidene complexes 7,8 and investigation of their reactivity toward various organic and organoelement compounds. 8,9 Recently discovered reactions of metal phosphinidene species of the new type related to the phosphinidene group transfer from the metal center attracted attention of researchers to the practical use of the nickel complexes in organic and organophos phorus synthesis 9-11 and made it possible to improve the methods for synthesis of biologically active compounds and useful ligands. An alternative method using the [R-P-W(CO) 5 ] intermediates (R = Ar, Alk) and in cluding the step of subsequent demetallation of the ob tained organophosphorus product 4,5,12 is less convenient.A possibility of the direct synthesis of free phosphiranes and phosphirenes has been demonstrated for the first time using as an example the relatively stable nickelphosphin idene complex 9 containing the sterically hindered ligand and the substituent at the phosphorus atom. 10,11 How ever, the synthesis of this complex is difficult and consists of several steps: the formation of primary phosphine [(dtbpe)Ni(P(H)dmp)] (dtbpe is 1,2 bis(di tert butyl phosphino)ethane, and dmp is 2,6 dimesitylphenyl), its subsequent oxidation with tropilium hexafluorophosphate, and further deprotonation with NaN(SiMe 3 ) 2 . 9 Thus, this method is more complicated than the known method for synthesis of phosphanorbornadiene, which prevents its wide propagation in the synt...

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Section: Resultsmentioning

confidence: 88%

Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

et al. 2007

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“…Both 1 e and 2 e reductions of [Ni(bpy) 3 ] 2+ , yielding [Ni(bpy) 3 ] + and [Ni(bpy) 3 ] 0 , respectively, have been reported as the initial electrochemical step in acetonitrile . Some reports suggest that [Ni(bpy) 3 ] 2+ and [Ni(bpy) 3 ] 0 undergo comproportionation to generate [Ni(bpy) 3 ] + , while others ignore this possibility, but conclude that the 2 e reduction product, [Ni(bpy) 3 ] 0 , is unstable and loses a bpy ligand . The overall mechanistic possibilities based on literature reports are shown in Scheme .…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Reduction of [Ni(Mebpy)₃]²⁺: Elucidation of the Redox Mechanism by Cyclic Voltammetry and Steady‐State Voltammetry in Low Ionic Strength Solutions

et al. 2020

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Bipyridine complexes of Ni are used as catalysts in a variety of reductive transformations. Here, the electroreduction of [Ni(Mebpy)3]2+ (Mebpy=4,4′‐dimethyl‐2,2′‐bipyridine) in dimethylformamide is reported, with the aim of determining the redox mechanism and oxidation states of products formed under well‐controlled electrochemical conditions. Results from cyclic voltammetry, steady‐state voltammetry (SSV) and chronoamperometry demonstrate that [Ni(Mebpy)3]2+ undergoes two sequential 1e reductions at closely separated potentials (E10’=−1.06±0.01 V and E20’=−1.15±0.01 V vs Ag/AgCl (3.4 M KCl)). Homogeneous comproportionation to generate [Ni(Mebpy)3]+ is demonstrated in SSV experiments in low ionic strength solutions. The comproportionation rate constant is determined to be >106 M−1 s−1, consistent with rapid outer‐sphere electron transfer. Consequentially, on voltammetric time scales, the 2e reduction of [Ni(Mebpy)3]2+ results in formation of [Ni(Mebpy)3]+ as the predominant species released into bulk solution. We also demonstrate that [Ni(Mebpy)3]0 slowly loses a Mebpy ligand (∼10 s−1).

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“…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].…”

Section: Synthesis Of Compounds With P-c Bondsmentioning

confidence: 99%

“…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]:…”

Section: Synthesis Of Compounds With P-c Bondsmentioning

confidence: 99%

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Electrocatalytic eco-efficient functionalization of white phosphorus

Budnikova

Yakhvarov

Sinyashin

2005

Journal of Organometallic Chemistry

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Cited by 25 publications

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Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

Electrochemical Reduction of [Ni(Mebpy)₃]²⁺: Elucidation of the Redox Mechanism by Cyclic Voltammetry and Steady‐State Voltammetry in Low Ionic Strength Solutions

Electrocatalytic eco-efficient functionalization of white phosphorus

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Cited by 25 publications

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Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

Electrocatalytic reduction of aryldichlorophosphines with the (2,2′-bipyridine)nickel complexes

Electrochemical Reduction of [Ni(Mebpy)3]2+: Elucidation of the Redox Mechanism by Cyclic Voltammetry and Steady‐State Voltammetry in Low Ionic Strength Solutions

Electrocatalytic eco-efficient functionalization of white phosphorus

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Electrochemical Reduction of [Ni(Mebpy)₃]²⁺: Elucidation of the Redox Mechanism by Cyclic Voltammetry and Steady‐State Voltammetry in Low Ionic Strength Solutions