AUTOXIDATION OF 3,5-DI-TERT-BUTYLCATECHOL CATALYZED BY 2 PYRAZOLATE-BRIDGED DICOPPER COMPLEXES WITH DIFFERENT STRUCTURAL FEATURES
AUTOXIDATION OF 3,5-DI-TERT-BUTYLCATECHOL CATALYZED BY 2 PYRAZOLATE-BRIDGED DICOPPER COMPLEXES WITH DIFFERENT STRUCTURAL FEATURES
复制标题
DOI：
10.1016/s0020-1693(00)80184-x
复制
发表时间：
1991-11-15
影响因子：
2.8
通讯作者：
URBACH, FL
中科院分区：
文献类型：
--
作者：
CHYN, JP;URBACH, FL
研究了两种吡唑酸桥接的二铜（II）配合物[Cu2(LEP)2]2+(1)和[Cu2(BLEP)(OH)]2+(2)作为3,5-二-丁基儿茶酚（DTBC）自氧化的催化剂。在1:1 CH3OH:H2O条件下，用初始速率法进行动力学研究，发现双核铜催化剂与O2反应具有一级速率规律，且与DTBC浓度无关。两种配合物催化的自氧化反应速率常数分别为[Cu2(BLEP)(OH)]2+的4.19 × 10(5) M-1 min-1和[Cu2(LEP)2]2+的4.65 × 10(3) M-1 min-1。2优越的催化活性归因于双核配体的存在，它保持了还原形式的二铜结构的完整性，并允许与O2更有利的相互作用模式。
Two pyrazolate-bridged dicopper(II) complexes, [Cu2(LEP)2]2+ (1) and [Cu2(BLEP)(OH)]2+ (2), have been studied as catalysts for the autoxidation of 3,5-di-t-butylcatechol (DTBC). Kinetic studies by the method of initial rates in 1:1 CH3OH:H2O revealed a rate law which is first order in the binuclear copper catalyst and O2 and independent of DTBC concentration. Rate constants for the autoxidations catalyzed by the two complexes are 4.19 x 10(5) M-1 min-1 for [Cu2(BLEP)(OH)]2+ and 4.65 x 10(3) M-1 min-1 for [Cu2(LEP)2]2+. The superior catalytic activity of 2 is attributed to the presence of the binucleating ligand which maintains the integrity of the dicopper structure in the reduced form and allows a more favorable mode of interaction with O2.