The catalytic efficiency of Ni(0) complexes in coupling reactions of organic and organoelemental halides is shown to be determined by the degree of charge transfer, the value of the electrochemical gap, and the availability or absence of competitive redox reactions. © 1997 Elsevier Science S.A

Budnikova Y.

Kargin Y.

Journal of Organometallic Chemistry

Kazan Federal University Digital Repository

Journal ofOfgan,9. metal l ic  Chemistry ELSEVIER Journal of Organometallic Chemistry 536-537 (1997) 265-272 The role of Ni(0) complexes in electrochemical phosphorylation of organic halides Part 1. Factors determining catalytic activity Yulia H. Budnikova a, Yuri M. Kargin b,. a Institute of Organic and Physical Chemist O' of RAg, ArbuzoL, st., 8, Kazan, 420083, Russia b . . . .  Kazan State Untverst~, Lemn st., 18, Kazan, 420008, Russta Received 24 June 1996; accepted 19 September 1996 Abstract The catalytic efficiency of Ni(0) complexes in coupling reactions of organic and organoelemental halides i  shown to be determined by the degree of charge transfer, the value of the electrochemical g p, and the availability orabsence of competitive r dox reactions. © 1997 Elsevier Science S.A. Keywords: Homogeneous redox catalysis; Ni(0) complexes; White phosphorus; Phosphorus chlorides; Electrochemistry 1. Introduction The elaboration of highly selective reactions leading to formation of carbon-carbon and carbon-element bonds is amongst the most important problems in the rapidly expanding area of metallocomplex catalysis. Organic halide functionalization can be achieved by the use of some organometallic compounds; however, tradi- tional chemical methods of catalyst regeneration are inconvenient because they demand stoichiometric amounts of reductants like zinc dust or Grignard reagents. Electrochemical methods for generation and regeneration of catalysts may work very productive in this respect, and in some instances one can obtain cross-coupling products from various halogen-contain- ing compounds or mercaptans and to carboxylate aryl- halides [1-6], and the like. Presently, one of the most important problems is to elucidate the factors determining catalyst reactivity and their quantitative evaluation. However, the mechanism of these reactions is not absolutely clear, causing trou- ble in the choices of optimal conditions and catalyst. We present here a brief overview of our recent work on electrochemical metallocomplex catalysis. We have * Corresponding author. To the memory of Professor Yu.T. Struchkov. 0022-328X/97/$17.00 © 1997 Elsevier Science S.A. All rights reserved. PII S0022- 3 28X(96)06784-8 succeeded in recent years in expanding the application area of familiar eactions of organic halide coupling on the basis of oxidative addition reactions. Thus, prelimi- nary data show that one can perform phosphorylation f some organic halides under the action of electrochemi- cally generated Ni complexes(0) with 7r-acceptor lig- ands using phosphorus chlorides [7,8] or white phospho- rus as phosphorylating a ents. Nickel complexes are very attractive catalysts because of their availability and ability to yield stable forms in low oxidation states (0, +1). The main objective of this paper is to find factors determining the reactivity of Ni(0) complexes in oxida- tive addition reactions and to use the information ob- tained to make an informed choice of the catalyst when performing the synthesis on a large scale. Among the other metals of the platinum group, nickel is noted for the least atomic size and d-orbital filling, resulting in a more effective display of electronic inter- actions between metal and ligand determining in many respects the catalytic ability of the complex. However, an analysis of the reduction process having regard to competitive homogeneous redox equilibria, limiting stages, calculation of rate and equilibrium constants i , in general, insufficient. Undoubtedly, a more compre- hensive concept of the complex reduction mechanism, its redox properties and electron interactions between 

The role of Ni(0) complexes in electrochemical phosphorylation of organic halides Part 1. Factors determining catalytic activity

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The role of Ni(0) complexes in electrochemical phosphorylation of organic halides Part 1. Factors determining catalytic activity

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