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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Dioxygen adducts of rhodium N-heterocyclic carbene complexes
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Dioxygen adducts of rhodium N-heterocyclic carbene complexes

机译：铑N-杂环卡宾配合物的双氧加合物

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摘要

Rhodium complexes functionalized by N-heterocyclic carbene ligands react with dioxygen to form adducts. Depending on the specifics of the ancillary ligands, oxygen binds to Rh either as a peroxide to form a fully oxidized Rh(iii) complex, or as singlet dioxygen in a Rh(i) square planar complex. We have shown through analysis of a series of compounds, some previously published and some novel, that the presence of additional ligands that would support the formation of an octahedral geometry, as typically found with Rh(iii) complexes, is critical for formation of the peroxide. In addition, we have demonstrated through DFT studies, that the potential energy surface with regard to the O-O bond length is relatively shallow, which provides a rationale for the distribution of bond lengths observed for apparently similar complexes analyzed by crystallography.
机译：由N-杂环卡宾配体官能化的铑配合物与双氧反应形成加合物。根据辅助配体的具体情况，氧以过氧化物的形式与Rh结合形成完全氧化的Rh（iii）配合物，或以Rh（i）方形平面配合物中的单重态双氧结合。通过对一系列化合物的分析，这些化合物先前已经发表，并且有些新颖，表明，通常存在Rh（iii）配合物的其他配体的存在将支持八面体几何结构的形成，这对于形成该化合物至关重要。过氧化物。另外，我们已经通过DFT研究证明，关于O-O键长的势能面相对较浅，这为通过晶体学分析的表观相似的配合物观察到的键长分布提供了理论依据。

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