Metal complex catalysis in organic electrosynthesis

Budnikova, Yu. G.

doi:10.1070/rc2002v071n02abeh000697

Cited by 56 publications

(29 citation statements)

References 170 publications

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“…3) can also be due to the reduction of a new compound (probably, an organo nickel intermediate) containing the nickel-phosphorus σ bond, as it was exemplified for some organic halides. 13,14 This peak corresponds, most likely, to the reduction of σ organonickel complex 1 formed via the oxidative addi tion of tippPCl 2 to the [Ni(bpy)] complex at one of the P-Cl bonds (Scheme 2).…”

Section: Methodsmentioning

confidence: 96%

“…These complexes are known as highly efficient catalysts of vari ous electrochemical coupling processes that allow one to synthesize organic and organophosphorus compounds of various types. [13][14][15] In some cases, the formation of phosphinidene particles, which act as intermediates of electrocatalytic processes involving organophosphorus re actants and white phosphorus, is detected in situ. 13,14 In the present work, we describe the reduction of aryldichlorophosphines PhPCl 2 and tippPCl 2 (tipp is 2,4,6 triisopropylphenyl) by the electrochemically gen erated [Ni(bpy) n ] complexes (n = 1, 2), affording highly reactive phosphorus containing intermediates that mani fest the properties of the phosphinidene complexes.…”

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confidence: 99%

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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: Methodsmentioning

confidence: 96%

mentioning

confidence: 99%

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

et al. 2007

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“…In addition, compared with the more conventional chemical cross-coupling methods, electrochemical reactions have the advantage of providing an additional driving force (cathodic potential) for the reaction processes, which thus limits the need for additional means of activation, such as heating of the reaction medium [85][86][87][88][89].…”

Section: Electrochemical Cross-coupling Using Ni-tpy Systemsmentioning

confidence: 99%

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

2018

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Abstract:In recent years, nickel has entered the stage for catalyzed C-C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2 :6 ,2 -terpyridine (tpy) stands as an excellent example of these ligands. This review summarizes research that has been devoted to exploring the mechanistic details in catalyzed C-C cross-coupling reactions using tpy-based nickel systems.

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“…From the viewpoint of implementation, electrochemical reactions have several advantages: mild conditions, high rates, selectivity, and convenient operational control through switching current density and potential. Electrochemical methods can be recommended for the preventive protection of the environment, because they do not require any special reagents [13][14][15][16][17][18][19][20][21][22][23][24][25][102][103][104].…”

Section: Electrocatalytic Ligand-directed Substitution Of C(sp 2 )-H mentioning

confidence: 99%

Redox-Induced Aromatic C–H Bond Functionalization in Metal Complex Catalysis from the Electrochemical Point of View

2017

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This review generalizes and specifies the oxidizing ability of a number of oxidants used in palladium (Pd)-catalyzed aromatic C-H functionalizations. The redox potentials have been analyzed as the measure of oxidant strength and applied to the reasoning of the efficiency of known reactions where catalytic cycles include cyclometalated palladium complexes (and other organopalladium key intermediates).

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Metal complex catalysis in organic electrosynthesis

Cited by 56 publications

References 170 publications

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

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

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Redox-Induced Aromatic C–H Bond Functionalization in Metal Complex Catalysis from the Electrochemical Point of View

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