Kinetics and mechanism of the oxidation of (.alpha.-hydroxyalkyl)chromium complexes by copper(II) and iron(III) ions
作者:Andreja Bakac、James H. Espenson
DOI:10.1021/ja00400a040
日期:1981.5
Copper(II) does not react with (..cap alpha..-alkoxyalkyl)chromium(2+) complexes at all, while iron(III) shows some reactivity with k'/sub Fe/ = 0.0127 s/sup -1/ (CrCH/sub 2/OCH/sub 3//sup 2 +/) and 0.0400 s/sup -1/ (CrCH(CH/sub 3/)OC/sub 2/H/sub 5//sup 2 +/), both in 1 M methanol. A mechanism proposed for the oxidation of (..cap alpha..-hydroxyalkyl)chromium(2+) complexesmore » by copper(II) and iron(III)
铜 (II) 和铁 (III) 离子与 (..cap α..-羟烷基) 铬 (2+) 络合物(烷基 = 甲基、乙基、2-丙基)在水或醇水溶液中反应导致裂解铬碳键。直接产物是 Cr/sup 2 +/、还原的金属离子(Cu/sup +/ 或 Fe/sup 2 +/)和相应的醛或酮。反应遵循速率定律 -d(CrROH/sup 2 +/)/dt = (k + k'(H)/sup -1/(CrROH/sup 2 +/)(M),其中 M = Cu/sup 2 +/ 或 Fe/sup 3 +/。主要的 k' 项在 1 M 含水母体醇(分别为甲醇、乙醇和 2-丙醇)中具有以下值: CrCH/sub 2/OH/sup 2 +/ , k'/sub Cu/ = 0.251 s/sup -1/,k'/sub Fe/ = 0.496 s/sup -1/; CrCH(CH/sub 3/)OH/sup 2 +/, 1.46