Preparation of Poly(1,4‐phenylene) by Nickel(0) complex catalyzed electropolymerization

Fauvarque, Jean‐François; Petit, Michel-Alain; Pflüger, Fernando; Jutand, Anny; Chevrot, C.; Troupel, Michel

doi:10.1002/marc.1983.030040703

Cited by 109 publications

(11 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…contradictions between our data (r < 0) 62 and the results of competitive experiments (r > 0); 28,55,[65][66][67][68][69] furthermore, it is excellent evidence for the conclusion on fast progression of the oxidative addition step. As it is known, electron-withdrawing groups accelerate a stoichiometric oxidative addition (r > 0), [74][75][76] which is completely consistent with data of the competitive experiments. At the same time, an acceleration of the rate-limiting step is promoted by electron-donating substituents in aryl iodides according to our data.…”

Section: Rate-limiting Step Of the Main Catalytic Cycle In The Heck Reaction With Aryl Iodidessupporting

confidence: 89%

Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol

Schmidt¹,

Halaiqa²,

Смирнов³

2006

Synlett

View full text Add to dashboard Cite

This account presents previous and recent mechanistic studies of the Heck reactions reported by the authors whose attention has been focused on a problem of the coupling of catalyst transformations within and without the catalytic cycle. Based on the understanding of the interaction mechanism between these processes a development of new methods of Heck chemistry became conceivable. In particular, such a rational approach allowed an elaboration of the ligand-free systems, which are effective not only in the reaction with non-activated aryl bromides but also with nonactivated aryl chlorides. 1 Introduction 2 Main Catalytic Cycle 2.1 Pd(0)/Pd(II) Catalytic Cycle 2.2 Rate-Limiting Step of the Main Catalytic Cycle in the Heck Reaction with Aryl Iodides 3 Reactions without the Main Catalytic Cycle of the Heck Reaction 3.1 Reduction of Palladium 3.2 Oxidation of Palladium 3.3 Agglomeration of Palladium 3.4 Dissolution of Palladium 3.5 Dissolution of Palladium as a Rate-Limiting Step of the Heck Reaction with Aryl Bromides 4 Coupling Effects of the Catalyst Reactions within and without the Main Catalytic Cycle 4.1 Reaction with Aryl Iodides 4.2 Reaction with Aryl Bromides and Aryl Chlorides 4.3 Reaction with the Heterogeneous Catalyst Precursors 5 Conclusions and Outlook

show abstract

Section: Rate-limiting Step Of the Main Catalytic Cycle In The Heck Reaction With Aryl Iodidessupporting

confidence: 89%

Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol

Schmidt¹,

Halaiqa²,

Смирнов³

2006

Synlett

View full text Add to dashboard Cite

show abstract

“…Use of 1,4-dichlorobenzene (Run 13) instead of 1,4-dibromobenzene produced poly(l,4-phenylene) in comparable yields. 10 9-10 9-10 9-10 9-10 6 -1 6-7 12-14 [14][15][16] Standard conditions: 10 mmol of monomer 1 ,4-dibromobenzene (I), or 4,4'-dibromobiphenyl (2), or 1 ,4-dichlorobenzene (3), or 1,3-dibromobenzene (4), or 2,7-dibromofluorene (5); 20 mmol of electrolyte: nBu,NBF, (1) or LiClO, (2), 1,5 mmol of CH,MgCl. T = 35 "C; vol.…”

Section: Monomer Effectmentioning

confidence: 99%

Electrosynthesis of poly(1,4‐phenylene) catalyzed by nickel complexes

et al. 1985

Self Cite

View full text Add to dashboard Cite

Conjugated polymers were prepared by electroreduction of aryl dihalides in presence of nickel complexes as catalysts. For instance, poly( I ,4-phenylene) was obtained from 4,4'-dibromobiphenyl in high yield (85%). According to the coupling mechanism and to IR spectra, the chains of the polymer are expected to have regular para-linkages and an average length ranging from 6 to I8 phenylene units. The effects of temperature, nature of monomer, catalyst and electrolyte on the yields and on the properties of the polymer were explored.

show abstract

“…[21] Ap ractical application of the nickelc atalysis by the Fauvarque group was represented by the synthesis of poly(1,4-phenylene) 2d from 1,4-dibromoarene 1d (Scheme 1d). [22] Subsequently,a lternative dihalo(hetero)arenes and even 1,2-diiodoethyne were successfully employedf or nickela-electroreductive coupling reactions to synthesized ifferent films and polymers. [23] While homo-coupling reactions have gained significant momentum, cross-electrophile couplings are more attractive, but at the same time significantly more challengingd ue to the full chemoselectivity control.…”

Section: Reductive Cross-electrophile Couplingmentioning

confidence: 99%

Evolution of High‐Valent Nickela‐Electrocatalyzed C−H Activation: From Cross(‐Electrophile)‐Couplings to Electrooxidative C−H Transformations

Zhang

Samanta

Vecchio

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

C−H activation has emerged as one of the most efficient tools for the formation of carbon–carbon and carbon–heteroatom bonds, avoiding the use of prefunctionalized materials. In spite of tremendous progress in the field, stoichiometric quantities of toxic and/or costly chemical redox reagents, such as silver(I) or copper(II) salts, are largely required for oxidative C−H activations. Recently, electrosynthesis has experienced a remarkable renaissance that enables the use of storable, safe and waste‐free electric current as a redox equivalent. While major recent momentum was gained in electrocatalyzed C−H activations by 4d and 5d metals, user‐friendly and inexpensive nickela‐electrocatalysis has until recently proven elusive for oxidative C−H activations. Herein, the early developments of nickela‐electrocatalyzed reductive cross‐electrophile couplings as well as net‐redox‐neutral cross‐couplings are first introduced. The focus of this Minireview is, however, the recent emergence of nickel‐catalyzed electrooxidative C−H activations until April 2020.

show abstract

Preparation of Poly(1,4‐phenylene) by Nickel(0) complex catalyzed electropolymerization

Cited by 109 publications

References 7 publications

Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol

Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol

Electrosynthesis of poly(1,4‐phenylene) catalyzed by nickel complexes

Evolution of High‐Valent Nickela‐Electrocatalyzed C−H Activation: From Cross(‐Electrophile)‐Couplings to Electrooxidative C−H Transformations

Contact Info

Product

Resources

About