a TGA substituent. A mechanism is proposed in which neutral TGA is unreactive, the (minor) thiolate form of the TGA monoanion undergoes one-electron oxidation by [Os(phen)(3)](3+) (k(c)), and the dianion of TGA likewise undergoes one-electron oxidation by [Os(phen)(3)](3+) (k(d)). The Marcus cross relationship provides a good account for the magnitude of k(d) in this and related reactions of TGA. [
[Os(phen)(3)](3+)(phen = 1,10-
菲咯啉)的
巯基乙酸(TGA)的
水氧化被痕量的Cu(2+)催化并被产物[Os]抑制(phen)(3)](2+)。在可以完全掩盖痕量Cu(2+)催化和自旋捕集PBN的二
吡啶甲酸(dipic)的存在下,已经研究了在pH2-1.82范围内的厌氧条件下的动力学。速率定律是-d [Os(phen)(3)(3 +)] / dt = k [TGA](tot)[Os(phen)(3)(3+)],其中k = 2 (k (b)K(a1)+ k(c)K(a1)K(i))[H(+)] + k(d)K(a1)K(a2)} / [H(+)]( 2)+ K(a1)[H(+)] + K(a1)K(a2)};K(a1)和K(a2)是TGA的连续酸解离常数,K(i)是两个TGA单阴离子的互变异构常数。k(b)+ k(c)K(i)=(5.9 +/- 0.3)x 10