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首页> 美国卫生研究院文献>other >A Model for Active-site Formation Process in DMSO Reductase Family Molybdenum Enzymes Involving Oxido-alcoholato- and Oxido-thiolato-molybdenum(VI) Core Structures
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A Model for Active-site Formation Process in DMSO Reductase Family Molybdenum Enzymes Involving Oxido-alcoholato- and Oxido-thiolato-molybdenum(VI) Core Structures

机译：DMSO还原酶家族钼酶涉及氧化-醇-氨基和氧化-硫代-钼（VI）核心结构的主动站点形成过程的模型。

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New bis(ene-1,2-dithiolato)-oxido-alcoholato-molybdenum(VI) and -oxido-thiolato-molybdenum(VI) anionic complexes, denoted as >[MoVIO(ER)L2]− (E = O, S; L = dimethoxycarboxylate-1,2-ethylenedithiolate), have been obtained from the reaction of the corresponding dioxido-moybdenum(VI) precursor complex with either an alcohol or a thiol in the presence of an organic acid (e.g. 10-camphorsulfonic acid) at low temperature. The >[MoVIO(ER)L2]− complexes have been isolated and characterized, and the structure of >[MoVIO(OR)L2]− has been determined by X-ray crystallography. The Mo(VI) center in >[MoVIO(OR)L2]− exhibits a distorted octahedral geometry with the two ene-1,2-dithiolate ligands being symmetry inequivalent. The computed structure of >[MoVIO(SR)L2]− is essentially identical to that of >[MoVIO(OR)L2]−. The electronic structures of the resulting molybdenum(VI) complexes have been evaluated using electronic absorption spectroscopy and bonding calculations. The nature of the distorted Oh geometry in these >[MoVIO(EEt)L2]− complexes results in a LUMO wavefunction that possesses strong π* interactions between the Mo(dxy) orbital and the cis S(pz) orbital localized on one sulfur donor from a single ene-1,2-dithiolate ligand. The presence of covalent Mo-Sdithiolene bonding interaction in these monooxido Mo(VI) compounds contributes to their low energy LMCT transitions. A second important d-p π bonding interaction derives from the ~180° Ooxo-Mo-E-C dihedral angle involving the alcoholate and thiolate donors, and this contributes to ancillary ligand contributions to the electronic structure of these species. The formation of >[MoVIO(OEt)L2]− and >[MoVIO(SEt)L2]− from the dioxidomolybdenum(VI) precursor may be regarded as a model for the active-site formation process that occurs in the DMSO reductase family of pyranopterin molybdenum enzymes.
机译：新的双（烯-1,2-二硫代Lato）-氧化-酒精-钼（VI）和-氧化-硫代-钼（VI）阴离子配合物，表示为> [Mo VI O（ ER）L2 ] -（E = O，S； L =二甲氧基羧酸盐-1,2-乙二硫醇盐），是通过相应的二氧化钼（VI）前体的反应获得的在低温下，在有机酸（例如10-樟脑磺酸）存在下，与醇或硫醇形成的配合物。分离并表征了> [Mo VI O（ER）L2 ] -配合物，并表征了> [Mo VI O（OR）L2 ] -已通过X射线晶体学测定。 > [Mo VI O（OR）L2] -中的Mo（VI）中心具有扭曲的八面体几何结构，其中两个ene-1， 2-二硫醇盐配体对称不等价。 > [Mo VI O（SR）L2] -的计算结构与> [Mo VI O（OR）L2 ] -。生成的钼（VI）配合物的电子结构已使用电子吸收光谱法和键合计算进行了评估。这些> [Mo VI O（EEt）L2] -配合物中扭曲的Oh几何的性质导致LUMO波函数具有强π * Mo（dxy）轨道和顺式S（pz）轨道之间的相互作用位于一个来自单个ene-1,2-二硫代配体的硫供体上。这些单氧化物Mo（VI）化合物中共价Mo-Sdithiolene键相互作用的存在有助于其低能LMCT跃迁。第二个重要的d-pπ键相互作用来自〜180°的Ooxo-Mo-E-C二面角，涉及醇盐和硫醇盐供体，这有助于这些物质的电子配体的辅助配体。 > [Mo VI O（OEt）L2] -和> [Mo VI O（来自二氧化钼（VI）前体的SEt）L2] -可以被视为吡喃蝶呤钼酶DMSO还原酶家族中发生的活性位点形成过程的模型。

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