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首页> 外文期刊>Chemistry: A European journal >Protonation of a Biologically Relevant Cu-II mu-Thiolate Complex: Ligand Dissociation or Formation of a Protonated Cu-I Disulfide Species?
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Protonation of a Biologically Relevant Cu-II mu-Thiolate Complex: Ligand Dissociation or Formation of a Protonated Cu-I Disulfide Species?

机译：生物相关的铜-II-硫杂酸盐复合物的质子化：配体离解或质子化的铜-I二硫化物物种的形成？

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摘要

The proton-induced electron-transfer reaction of a Cu-II mu-thiolate complex to a Cu-I-containing species has been investigated, both experimentally and computationally. The Cu-II mu-thiolate complex [Cu-II 2(LMeS) 2] 2+ is isolated with the new pyridyl-containing ligand LMeSSLMe, which can form both Cu-II thiolate and Cu-I disulfide complexes, depending on the solvent. Both the Cu-II and the Cu-I complexes show reactivity upon addition of protons. The multivalent tetranuclear complex [Cu-I 2Cu(II) 2(LS) 2(CH3CN)(6)](4+) crystallizes after addition of two equivalents of strong acid to a solution containing the mu-thiolate complex [Cu-II (2)((LS)-S-Me)(2)](2+) and is further analyzed in solution. This study shows that, upon addition of protons to the Cu-II thiolate compound, the ligand dissociates from the copper centers, in contrast to an earlier report describing redox isomerization to a Cu-I disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated Cu-II mu-thiolate and Cu-I disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [Cu-I(CH3CN)(4)](+) and protonated ligand is energetically favored over conversion to a protonated Cu-I disulfide complex.
机译：已经通过实验和计算研究了质子诱导的Cu-II亩-硫醇盐配合物与含Cu-I的物质的电子转移反应。用新的含吡啶基的配体LMeSSLMe分离了Cu-II mu-硫醇盐络合物[Cu-II 2（LMeS）2] 2+，根据溶剂的不同，它们可以同时形成Cu-II硫醇盐和Cu-I二硫化物络合物。 Cu-II和Cu-I配合物在添加质子时均显示出反应性。多价四核配合物[Cu-I 2Cu（II）2（LS）2（CH3CN）（6）]（4+）在将两当量的强酸添加到含mu-硫醇盐配合物[Cu-II （2）（（LS）-S-Me）（2）]（2+），并在溶液中进一步分析。这项研究表明，将质子添加到Cu-II硫醇盐化合物后，配体会从铜中心解离，这与先前报道的氧化还原异构化为在吡啶基部分质子化的Cu-I二硫化物的相反。用LSSL对质子化的Cu-II巯基硫酸盐和Cu-I二硫化物物种的计算研究表明，在添加两个当量的质子时，配体解离形成[Cu-I（CH3CN）（4）]（+）和质子化的配体在能量上优于转化为质子化的Cu-1二硫化物络合物。

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