Constructing synthetic models of the Mo/Cu active site of aerobic carbon monoxide dehydrogenase (CODH) has been a long-standing synthetic challenge thought to be crucial for understanding how atmospheric concentrations of CO and CO2 are regulated in the global carbon cycle by chemolithoautotrophic bacteria and archaea. Here we report a W/Cu complex that is the closest synthetic mimic constructed to date, enabled by a silyl protection/deprotection strategy that provided access to a kinetically stabilized complex with mixed O2-/S2- ligation between (bdt)(O)WVI and CuI(NHC) (bdt = benzene dithiolate, NHC = N-heterocyclic carbene) sites. Differences between the inorganic core's structural and electronic features outside the protein environment relative to the native CODH cofactor point to a biochemical CO oxidation mechanism that requires a strained active site geometry, with Lewis acid/base frustration enforced by the protein secondary structure. This new mecha-nistic insight has the potential to inform synthetic design strategies for multimetallic energy storage catalysts.

中文翻译：

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好氧 CODH 的 Mo/Cu 辅因子的 AW/Cu 合成模型表明，生化 CO 氧化需要受挫的路易斯酸/碱对

构建好氧一氧化碳脱氢酶 (CODH) 的 Mo/Cu 活性位点的合成模型一直是一项长期存在的合成挑战，被认为对于理解化学自养细菌和化学自养细菌在全球碳循环中如何调节大气中 CO 和 CO2 的浓度至关重要。古细菌。在这里，我们报告了一种 W/Cu 复合物，它是迄今为止构建的最接近的合成模拟物，通过甲硅烷基保护/去保护策略实现，该策略提供了对 (bdt)(O)WVI 之间混合 O2-/S2- 连接的动力学稳定复合物的访问和CuI（NHC）（bdt =苯二硫醇盐，NHC = N-杂环卡宾）位点。无机核之间的差异' 相对于天然 CODH 辅因子而言，蛋白质环境之外的结构和电子特征指向一种生化 CO 氧化机制，该机制需要应变的活性位点几何形状，而路易斯酸/碱受阻由蛋白质二级结构强制执行。这种新的机制洞察力有可能为多金属储能催化剂的合成设计策略提供信息。