The oxidation of ascorbic acid by tris(2,2′-bipyridine) complexes of osmium(III), ruthenium(III) and nickel(III) in aqueous media: Applications of the Marcus cross-relation
作者:Donal H. Macartney、Norman Sutin
DOI:10.1016/s0020-1693(00)81430-9
日期:1983.1
oxidation of L-ascorbic acid (H2A) by tris(2,2′-bypyridine) and tris-(4,4′-dimethyl-2,2′-bipyridine) complexes of osmium(III), ruthenium(III), and nickel(III) have been investigated in acidic aqueous media at 9–25 °C. The observed inverse acid dependence, -d[ML3+3]/dt = 2(k1 + k2K1/[H+])(ML3+3][H2A], suggest a mechanism involving H2A and HA− pathways, for which the specific rate and activation parameters
s(3,2,2'-bypyridine)和tris-(4,4'-dimethyl-2,2'-bipyridine)配合物对L-抗坏血酸(H 2 A)外球氧化的动力学III),钌(III)和镍(III)已在9–25°C的酸性水性介质中进行了研究。观察到的反酸依赖性-d [ML 3+ 3 ] / dt = 2(k 1 + k 2 K 1 / [H + ])(ML 3+ 3 ] [H 2 A],表明涉及H 2的机理A和HA -已经确定了具体速率和激活参数的途径。这些和以前报道的涉及抗坏血酸物质的交叉反应速率常数在马库斯关系方面是相关的。单电子对的自交换参数的估计:H 2 A / H 2 A + ·,k 11 = 2×10 3 M - s -1 ; HA - / HA·,K 11 = 1×10 5 中号-小号-1 ; A 2- / A-·,k 11 = 2×10 5 M - s -1,根据由质子和