10170-69-1 Heterobimetallic compl431-03-8 Facile Synthesis of α-Keto Carbonyl Compounds by Indirect Anodic Oxidationexes of rhodium dibenzotetramethylaza[14]annulene [(tmtaa)RH-M]: Formation, structures, and bond dissociation energetics

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A rhodium(II) dibenzotetramethylaza[14]annulene dimer ([(tmtaa)Rh]2) undergoes metathesis reactions with [CpCr(CO)3]2, [CpMo(CO)3]2, [CpFe(CO)2]2, [Co(CO)4]2, and [Mn(CO)5]2 to form (tmtaa)Rh-M complexes (M = CrCp(CO)3, MoCp(CO)3, FeCp(CO)2, Co(CO)4, or Mn(CO)5). Molecular structures were determined for (tmtaa)Rh-FeCp(CO)2, (tmtaa)Rh-Co(μ-CO)(CO)3, and (tmtaa)Rh-Mn(CO)5 by X-ray diffraction. Equilibrium constants measured for the metathesis reactions permit the estimation of several (tmtaa)Rh-M bond dissociation enthalpies (Rh-Cr = 19 kcal mol-1, Rh-Mo = 25 kcal mol-1, and Rh-Fe = 27 kcal mol-1). Reactivities of the bimetallic complexes with synthesis gas to form (tmtaa)Rh-C(O)H and M-H are surveyed. https://www.lookchem.com/CASDataBase_10170-69-1.htm Secondary alcohols having a carbonyl group at the neighboring carbon atom were electrochemically oxidized to the corresponding α-keto carbonyl compounds in good yields.Thus, aromatic α-hydroxyl esters were easily transformed to arylglyoxylates in excellent yields using an undivided cell while efficient anodic oxidation of α-hydroxyl ketones and aliphatic α-hydroxyl esters successfully proceeded in a divided cell to give the corresponding α-keto carbonyl compounds. https://www.lookchem.com/CASDataBase_431-03-8.htm

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