Transformation of Nitrile to Cyanide and Aldehyde Using a Cobalt(II) Complex and Dioxygen

Abstract

Canning a carbon: During oxidation with O2, the cobalt(II) complex [Co(salmdpt)] (salmdptH2=bis[3‐(salicylideneimino)‐propyl]methylamine) reacts with a nitrile substrate to form the cyanide complex [Co(salmdpt)CN] (see structure) and the corresponding aldehyde, which contains one less carbon atom than the starting nitrile.

Synthesis and structure of mono-, bi- and trimetallic amine-bis(phenolate) cobalt(ii) complexes

“…For example, salen coordination compounds of Co II and Co III have been utilized as catalysts for coupling and copolymerization of carbon dioxide with epoxides, [49][50][51][52][53][54] and homopolymerization of epoxides. 55- 57 Also, interesting stoichiometric oxidation chemistry using Co II salen complexes has been reported, 58 and Co II phthalocyanine compounds are known to mediate catalytic aerobic oxidation of a range of organic substrates. 59, 60 Herein we report the preparation, structure determination and properties of mono-, bi-and trimetallic cobalt complexes of the sterically hindered tetradentate tripodal ligands, [O 2 NN¢] BuMeNMe2 , [O 2 NN¢] BuBuNMe2 , [O 2 NN¢] AmAmNEt2 and [O 2 NN¢] AmAmPy (Fig.…”

Distinct Reactivity of a Mononuclear Peroxocobalt(III) Species toward Activation of Nitriles

“…However, only one example of nitrile group activation by peroxometal complexes has been reported so far: the peroxopalladium­(II) complexes that react with CH 3 CN (MeCN) to give peroxometallacycle products . Recently, hydroperoxocobalt­(III) species has been proposed to be a reactive intermediate for the CH bond activation of nitriles . Herein, we report an entirely new type of nitrile group activation in which the mononuclear side-on peroxocobalt­(III) complex, [Co III (TBDAP)­(O 2 )] + ( 1 ; TBDAP = N , N -di- tert -butyl-2,11-diaza­[3.3]­(2,6)-pyridinophane), reacts with nitrile derivatives (RCN; R = Me, Et, and Ph) in a dioxygenase-like manner to afford a series of hydroximatocobalt­(III) complexes, [Co III (TBDAP)­(R-C­(NO)­O)] + where R = Me ( 2 ), Et ( 3 ), and Ph ( 4 ) (Scheme ).…”

“…16 Recently, hydroperoxocobalt(III) species has been proposed to be a reactive intermediate for the CH bond activation of nitriles. 17 ). The one-pot activation of nitriles through 1, which is readily accessible by reaction of a cobalt(II) precursor with H 2 O 2 and triethylamine (TEA), could offer practical applications.…”

Syntheses and characterisation of tris(3-(pyridin-2-yl)-1H-pyrazol-1-yl)methane and its bis(µ-hydroxo) dicobalt(II) complex

“…4 Furthermore, stoichiometric applications like the transformation of nitriles to aldehydes or cyanides have been subject of considerable interest. 5 By substitution of the base with excess sodium carbonate the yield could be considerably enhanced. A multitude of ligands have been synthesised according to this method, e.g.…”