The synthesis, spectroscopy, crystal structure, and electrochemical behavior of cis-β-Ru^II(CO)₂, cis-β-Ru^II(CO)(H₂O), and cis-β-Ru^II(CO)(carbene) complexes supported by sterically bulky salen ligands are described, along with the catalytic activity of chiral cis-β-[Ru^II(salen)(CO)₂] complexes toward enantioselective carbene Si–H insertion using N₂C(Ar)CO₂R as the carbene source under light irradiation with product yields up to 96% and ee up to 84%. The cis-β-Ru^II(CO)(H₂O) complex was isolated by using a binaphthyl salen ligand bearing bulky CPh₃ substituents with the H₂O molecule coordinated at the site trans to an N_imine atom of the salen ligand. Light irradiation of a cis-β-Ru^II(CO)₂ complex, supported by a binaphthyl salen ligand with ^tBu substituents, followed by treatment with N₂CAr₂ (Ar = Ph, p-ClC₆H₄) gave cis-β-[Ru^II(salen)(CO)(CAr₂)], which features a coordinated carbene ligand trans to a salen N_imine atom and undergoes carbene transfer to nitrosobenzene to give the corresponding nitrone product. These findings and related HR-ESI-MS studies provide evidence for the involvement of salen-supported cis-β-Ru^II(CO)(C(Ar)CO₂R) active species in the intermolecular carbene Si–H insertion reaction catalyzed by cis-β-[Ru^II(salen)(CO)₂] complexes.

中文翻译：

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带有大体积Salen配体的顺式-β-钌配合物：对映选择性分子间碳原子插入Si-H键和X-射线晶体结构的顺式-β- [Ru ^II（salen）（CO）（CPh ₂）]配合物

合成，光谱，晶体结构和电化学行为顺式β-钌^II（CO）₂，顺式β-钌^II（CO）（H ₂ O），和顺式β-钌^II（CO）（卡宾）描述了由体积庞大的Salen配体支持的配合物，以及使用N ₂ C（Ar）CO ₂的手性顺式β- [Ru ^II（salen）（CO）₂ ]配合物对对映选择性卡宾Si–H插入的催化活性。在光照射下，R作为卡宾源，产品收率高达96％，ee高达84％。该顺β-茹^II（CO）（H ₂ O）络合物是通过使用带有庞大CPh ₃取代基的双萘基Salen配体进行分离的，其中H ₂ O分子在与SALEN配体的N_亚胺原子反位的位点配位。在具有^t Bu取代基的双萘基Salen配体的支持下，对顺-β- Ru ^II（CO）₂络合物进行光照射，然后用N ₂ CAr ₂（Ar = Ph，p -ClC ₆ H ₄）处理，得到顺- β- [Ru ^II（salen）（CO）（CAr ₂）]，其特征在于将配位的卡宾配体反式转化为Salen N_亚胺原子，并将卡宾转移至亚硝基苯，得到相应的硝酮产物。这些发现和相关的HR-ESI-MS研究提供了萨伦支持的参与证据顺式β-钌^II（CO）（C（Ar）的CO ₂ R）在分子间卡宾活性种的Si-H插入反应催化顺式-β- [Ru ^II（salen）（CO）₂ ]配合物。