ESE-ENDOR and ESEEM Characterization of Water and Methanol Ligation to a Dinuclear Mn(III)Mn(IV) Complex†
ESE-ENDOR and ESEEM Characterization of Water and Methanol Ligation to a Dinuclear Mn(III)Mn(IV) Complex†
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水和甲醇连接双核 Mn(III)Mn(IV) 配合物的 ESE-ENDOR 和 ESEEM 表征†
DOI：
10.1021/ja963682s
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发表时间：
1997
影响因子：
15
通讯作者：
R. Britt
中科院分区：
文献类型：
--
作者：
D. Randall;A. Gelasco;M. Caudle;V. Pecoraro;R. Britt
用1H电子自旋回波（ESE）-电子核双共振（ENDOR）和1H和2 H ESE包络调制（ESEEM）研究了水和甲醇与混合价Mn（III）Mn（IV）配合物的相互作用.（2-OH-3，5-Cl 2-SALPN）2 Mn（III）Mn（IV）络合物的衍生物是金属蛋白中水与多核Mn络合物结合的结构和光谱建模的理想选择，特别是光系统II（PSII）和锰过氧化氢酶（MnCat）。使用ESE-ENDOR和ESEEM技术，1H超精细参数确定为水和甲醇连接到Mn（III）离子的复杂。水的质子直接绑定到Mn（III）是不等价的，并表现出大致轴向偶极超精细相互作用（Tdip = 8.4 MHz和Tdip = 7.4 MHz），允许使用一个模型来确定方向和径向距离，其中质子经历一个点偶极与每个Mn离子的相互作用。一般方程给出的菱形偶极超精细相互作用的组件之间的p…
Interactions of water and methanol with a mixed valence Mn(III)Mn(IV) complex are explored with 1H electron spin echo (ESE)-electron nuclear double resonance (ENDOR) and 1H and 2H ESE envelope modulation (ESEEM). Derivatives of the (2-OH-3,5-Cl2-SALPN)2 Mn(III)Mn(IV) complex are ideal for structural and spectroscopic modeling of water binding to multinuclear Mn complexes in metalloproteins, specifically photosystem II (PSII) and manganese catalase (MnCat). Using ESE-ENDOR and ESEEM techniques, 1H hyperfine parameters are determined for both water and methanol ligated to the Mn(III) ion of the complex. The protons of water directly bound to Mn(III) are inequivalent and exhibit roughly axial dipolar hyperfine interactions (Tdip = 8.4 MHz and Tdip = 7.4 MHz), permitting orientations and radial distances to be determined using a model where the proton experiences a point dipole interaction with each Mn ion. General equations are given for the components of the rhombic dipolar hyperfine interaction between a p...