Internal carbon monoxide exchange and CO dissociation in cobalt carbonyl carbene complexes. A density functional study

Low-Temperature Synthesis of CoO Nanoparticles via Chemically Assisted Oxidative Decarbonylation

“…Two different structures were located for the Co 2 (CO) 7 -trimethylamine oxide adducts ( Co 2 (CO) 7 ·TMAO-ax and Co 2 (CO) 7 ·TMAO-eq ). They differ in the position (axial or equatorial) occupied by the TMAO ligand and, according to the known fluxional behavior of cobalt carbonyl complexes, they should readily interconvert at room temperature. According to the calculated B3LYP energies, the equatorial adduct Co 2 (CO) 7 ·TMAO-eq will importantly predominate in solution (Δ E eq/ax = −1.33 kcal/mol).…”

DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation

“…For Co 2 (CO) 8 , as a catalyst precursor, the reaction leading to diethyl malonate was found to occur in two different cycles. In the first one, the coordinatively unsaturated Co 2 (CO) 7 serves as the active catalyst, which forms the bridging carbonyl–carbene complex Co 2 (CO) 7 (CHCOOEt) after its reaction with EDA [ 17 , 18 ]. The catalytic cycle can go on with an intramolecular ketene formation and eventually the release of ketene, or with the dissociation of a terminal CO ligand giving rise to the unsaturated Co 2 (CO) 6 (CHCOOEt), which is also able to react with diazoalkanes, opening the second catalytic cycle [ 19 ].…”