Functional Analogue Reaction Systems of the DMSO Reductase Isoenzyme Family: Probable Mechanism of <i>S</i>-Oxide Reduction in Oxo Transfer Reactions Mediated by Bis(dithiolene)−Tungsten(IV,VI) Complexes
作者:Kie-Moon Sung、R. H. Holm
DOI:10.1021/ja012735p
日期:2002.4.1
development of structural and functional analogues of the DMSO reductase family of isoenzymes allows mechanistic examination of the minimal oxygen atom transfer paradigm M(IV) + QO M(VI) O + Q with the biological metals M = Mo and W. Systematic variation of the electronic environment at the WIV center of desoxo bis(dithiolene) complexes is enabled by introduction of para-substituted phenyl groups in the
DMSO 还原酶同工酶家族的结构和功能类似物的最新发展允许对最小氧原子转移范式 M(IV) + QO M(VI) O + Q 与生物金属 M = Mo 和 W 进行机械检查。 系统变异通过在赤道 (eq) 二硫烯配体和轴向 (ax) 苯酚配体中引入对位取代的苯基,可以实现脱氧双 (二硫烯) 配合物 WIV 中心的电子环境。化合物 [W(CO)2(S2C2(C6H4-pX)2)2] (54-60%) 已通过从 [Ni(S2C2(C6H4-pX)2)2] 到 [W(CO) )3(MeCN)3]。一系列 25 种复合物 [W(IV)(OC6H4-p-X')(S2C2(C6H4-pX)2)2]1- ([X4,X'], X = Br, F, H, Me, OMe ; X' = CN, Br, H, Me, NH2; 41-53%) 已通过五个二羰基配合物与五个酚盐配体的配体取代获得。对于电子转移系列