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Copper(II) complexes of tripodal ligand scaffold (N3O) as functional models for phenoxazinone synthase
Journal of Inorganic Biochemistry ( IF 3.9 ) Pub Date : 2020-11-21 , DOI: 10.1016/j.jinorgbio.2020.111313
Winaki P Sohtun 1 , Sethuraman Muthuramalingam 2 , Muniyandi Sankaralingam 3 , Marappan Velusamy 1 , Ramasamy Mayilmurugan 2
Affiliation  

The copper(II) complexes [Cu(L)NO3] (1–9) of newer N3O ligands (L1 -L9) have been synthesized and characterized. The molecular structure of 1, 4, and 7 exhibited nearly a perfect square pyramidal geometry (τ, 0.04–0.11). The Cu-OPhenolate bonds (~ 1.91 Å) are shorter than the Cusingle bondN bonds (~ 2.06 Å) due to the stronger coordination of anionic phenolate oxygen. The Cu(II)/Cu(I) redox potentials of 19 appeared around −0.102 to −0.428 V versus Ag/Ag+ in water. The electronic spectra of the complexes showed the d-d transitions around 643–735 nm and axial EPR parameter (g||, 2.243–2.270; A||, 164–179 × 10−4 cm−1) that corresponds to square pyramidal geometry. The bonding parameters α2, 0.760–0.825; β2, 0.761–0.994; γ2, 0.504–0.856 and K||, 0.698–0.954 and K, 0.383–0.820 calculated from EPR spectra and energies of d-d transitions. The complexes catalyzed the conversion of substrate 2-aminophenol into 2-aminophenoxazine-3-one using molecular oxygen in the water and exhibited the yields of 41–61%. The formation of the product is accomplished by the appearance of a new absorption band at 430 nm and the rates of formation were calculated as 6.98–15.65 × 10−3 s−1 in water. The reaction follows Michaelis-Menten enzymatic reaction kinetics with turnover numbers (kcat) 9.11 × 105 h−1 for 1 and 4.66 × 105 h−1 for 9 in water. The spectral, redox and kinetic studies were performed in water to mimic the enzymatic oxidation reaction conditions.



中文翻译:

三足配体支架 (N3O) 的铜 (II) 复合物作为吩恶嗪酮合酶的功能模型

新型 N 3 O 配体 ( L1 -L9 )的铜 (II) 配合物 [Cu( L )NO 3 ] ( 1–9 ) 已被合成和表征。的分子结构1图4,7几乎表现出完美的方锥体几何形状(τ,0.04-0.11)。由于阴离子酚盐氧的配位更强,Cu-O酚盐键 (~ 1.91 Å) 比 Cu N 键 (~ 2.06 Å)短。19的 Cu(II)/Cu(I) 氧化还原电位出现在 -0.102 至 -0.428 V 与 Ag/Ag +单键在水里。复合物的电子光谱显示在 643-735 nm 附近的 dd 跃迁和轴向 EPR 参数(g ||,2.243-2.270;A ||, 164-179 × 10 -4  cm -1)对应于方形金字塔几何形状。键合参数α 2,0.760-0.825;β 2 , 0.761–0.994; γ 2 , 0.504–0.856 和K || , 0.698–0.954 和K , 0.383–0.820 从 EPR 光谱和 dd 跃迁的能量计算。该配合物利用水中的分子氧催化底物 2-氨基苯酚转化为 2-氨基吩恶嗪-3-one,产率为 41-61%。产物的形成是通过在 430 nm 处出现新的吸收带来完成的,并且在水中的形成速率计算为 6.98–15.65 × 10 -3  s -1。该反应用如下的转换数(米氏酶促反应动力学ķ)9.11×10 5  ħ -11和4.66×10 5  ħ -19在水里。在水中进行光谱、氧化还原和动力学研究以模拟酶促氧化反应条件。

更新日期:2020-11-22
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