Thermal decomposition of derivatives of organocobalt(III)

μ-Polymethylene bridged dicobaloximes: Structural, photolysis and thermal decomposition properties

“…This process is mainly the cleavage of axial ligands, but accompanying the decomposition of part equatorial ligand. The elimination of HNO 2 at this stage is confirmed by the test with sulfanilicacid and a-naphthylamine [33]. The second transition (280-500°C) involves the decomposition of the common ÔcoreÕ complexes (bis(dimethylglyoximato)cobalt(II)) [33,34].…”

“…In the range of 150-500°C, the thermal decomposition of the dicobaloximes 1-4 includes two transitions. The first transition of 1-4 (150-280°C) corresponds to a loss of two axial pyridine ligands, a polymethylene and four HNO 2 molecules [33,34]. This process is mainly the cleavage of axial ligands, but accompanying the decomposition of part equatorial ligand.…”

Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

“…Square planar Co or Ni complexes generate excellent nucleophiles upon reduction that react with alkyl iodides or bromides [39–48] . The organocobalt intermediates that result from these substitution reactions are known to undergo subsequent Co‐alkyl bond homolysis at elevated temperatures [49–52] . The resulting carbon‐centered radicals can be functionalized through a variety of transformations to deliver value‐added products, but few methodologies rely on alkyl chlorides as the source of these key radical intermediates and even fewer utilize electrochemistry [2,38] .…”

“…[39][40][41][42][43][44][45][46][47][48] The organocobalt intermediates that result from these substitution reactions are known to undergo subsequent Co-alkyl bond homolysis at elevated temperatures. [49][50][51][52] The resulting carbon-centered radicals can be functionalized through a variety of transformations to deliver value-added products, but few methodologies rely on alkyl chlorides as the source of these key radical intermediates and even fewer utilize electrochemistry. [2,38] In particular, electrochemical reactions catalyzed by Co or Ni with chloroalkyl electrophiles are generally limited to activated derivatives like benzyl chloride or chloroacetonitrile and to methodologies like protodechlorination.…”

An Efficient Method for the Synthesis of 5-Arylisoxazoles from Benzyl Cobaloximes Using Microwave Irradiation

“…The Co-C bond of organocobaloximes is weak, and its cleavage is achieved by light or heat exposure [5][6][7][8][9][10][11]. Brown et al first reported the thermal decomposition of benzyl cobaloximes (a reflux period is 24-48 h) for the synthesis of 5-arylisoxazoles [8].…”