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[四甲基铵](镍（II）（双乙酰胺基乙胺））：一种镍超氧化物歧化酶的合成模型，其中镍处于混合胺/酰胺配位环境中。

[Me4N](Ni(II)(BEAAM)): a synthetic model for nickel superoxide dismutase that contains Ni in a mixed amine/amide coordination environment.

作者信息

Shearer Jason, Zhao Ningfeng

机构信息

Department of Chemistry/216, University of Nevada, Reno, Reno, Nevada 89557, USA.

出版信息

Inorg Chem. 2006 Nov 27;45(24):9637-9. doi: 10.1021/ic061604s.

DOI:10.1021/ic061604s
PMID:17112256
Abstract

Nickel superoxide dismutase (NiSOD) is a metalloenzyme that converts O2*- into H2O2 and O2 by cycling between Ni(II) and Ni(III) oxidation states. Reduced NiSOD contains Ni(II) in a square-planar N2S2 coordination environment formed by two cysteinate S atoms, an amide N, and an amine N to Ni(II). Me4N represents the first NiN2S2 complex containing Ni in a mixed amine/amide environment. Me4 contains Ni-S bonds at 2.177(2) and 2.137(2) A and Ni-N bonds at 1.989(7) and 1.858(6) A, which compare well with the metalloenzyme. Orange solutions of Me(4)N in MeCN are diamagnetic and stable toward O2 for weeks. A quasireversible Ni(II/III) redox couple is observed for Ni(II)(BEAAM) at 0.12(1) V vs Ag/AgCl. These data suggest that NiSOD utilizes the mixed amine/amide ligands to modulate the Ni(II/III) redox couple to best match the O2*- reduction/oxidation couples while maintaining O2 stability.

摘要

镍超氧化物歧化酶（NiSOD）是一种金属酶，它通过在Ni（II）和Ni（III）氧化态之间循环，将超氧阴离子转化为过氧化氢和氧气。还原态的NiSOD在由两个半胱氨酸的硫原子、一个酰胺氮和一个胺氮与Ni（II）形成的平面正方形N2S2配位环境中含有Ni（II）。Me4N代表了第一个在混合胺/酰胺环境中含有Ni的NiN2S2配合物。Me4含有键长为2.177(2)和2.137(2) Å的Ni-S键以及键长为1.989(7)和1.858(6) Å的Ni-N键，这与金属酶的情况相当。Me(4)N在乙腈中的橙色溶液是抗磁性的，并且对氧气稳定数周。对于Ni(II)(BEAAM)，相对于Ag/AgCl在0.12(1) V处观察到一个准可逆的Ni(II/III)氧化还原对。这些数据表明，NiSOD利用混合胺/酰胺配体来调节Ni(II/III)氧化还原对，以最佳匹配超氧阴离子的还原/氧化对，同时保持对氧气的稳定性。

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