Catalytic reduction of cyclohexanecarbonyl chloride with electrogenerated nickel(I) salen in acetonitrile

Catalytic reduction of 1-iodooctane by nickel(I) salen electrogenerated at carbon cathodes in dimethylformamide: Effects of added proton donors and a mechanism involving both metal- and ligand-centered one-electron reduction of nickel(II) salen

“…In a study of the nickel(I) salen-mediated reduction of a,x-dihaloalkanes [44], it was determined that alkyl radicals undergo both coupling and disproportionation, as well as hydrogen-atom abstraction from the solvent, to form the observed products. Polymer-bound nickel(I) salen has been shown to catalyze the reductions of several alkyl halides [43,45], whereas solution-phase nickel(I) salen induces the reductive coupling of ethylene halohydrins [46], the reduction of cyclohexanecarbonyl chloride [47], the addition of alkyl radicals to activated olefins [48], the electroreductive intramolecular cyclizations of 6-bromo-1-hexene [50] and haloalkynes [61], the catalytic reduction of 1-bromooctane at a mercury cathode [52], and the catalytic acetoxylation of 1,6-dihalohexanes in the presence of acetic acid [57]. Other investigations have entailed the use of electrogenerated nickel(I) salen in an ionic liquid [51] as well as the stoichiometric reaction between an alkyl halide and nickel(I) salen (in the presence of dioxygen, water, and light) to afford an aldehyde [54,56] or ketone [60].…”

Stoichiometric reduction of primary alkyl monohalides with electrogenerated nickel(I) salen: Formation of aldehydes

“…For a number of years, our laboratory has been interested in the catalytic reduction of alkyl halides by [[2,2 0 -[1,2-ethanediylbis(nitrilomethylidyne)]bis[phenolato]]-N,N 0 ,O,O 0 ]nickelate(I) -hereafter called nickel(I) salen -electrogenerated from nickel(II) salen at mercury and carbon cathodes [18][19][20][21][22][23][24]. For example, the products derived from the interaction between 6-bromo-1-hexene and electrogenerated nickel(I) salen in acetonitrile containing tetramethylammonium tetrafluoroborate are methylcyclopentane (18%), 1,2-dicyclopentylethane (37%), 7-cyclopentylhept-1-ene (13%), 1,11-dodecadiene (1%), and 1-hexene (1%) [24].…”

A novel copper(ii) complex with an unsymmetrical tridentate-Schiff base: synthesis, crystal structure, electrochemical, morphological and electrocatalytic behaviors toward electroreduction of alkyl and aryl halides

“…7A). 45 Also, the electropolymerized lms of poly-(Cu(L)(Py)(ClO 4 )) were found to be effective for the electrocatalytic reduction of bromocyclopentane and iodobenzene. Cyclic voltammograms obtained on glassy carbon electrode, coated with a polymerized lm of poly-(Cu(L)(Py)(ClO 4 )) in DMF solution, are illustrated in Fig.…”