当前位置：
X-MOL 学术
›
Dalton Trans.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Effects of silylene ligands on the performance of carbonyl hydrosilylation catalyzed by cobalt phosphine complexes
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-04-18 , DOI: 10.1039/d3dt00372h
Qingqing Fan 1 , Xinyu Du 1 , Wenjing Yang 1 , Qingshuang Li 1 , Wei Huang 1 , Hongjian Sun 1 , Alexander Hinz 2 , Xiaoyan Li 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-04-18 , DOI: 10.1039/d3dt00372h
Qingqing Fan 1 , Xinyu Du 1 , Wenjing Yang 1 , Qingshuang Li 1 , Wei Huang 1 , Hongjian Sun 1 , Alexander Hinz 2 , Xiaoyan Li 1
Affiliation
|
In order to study the effects of silylene ligands on the catalytic activity of carbonyl hydrosilylation catalyzed by cobalt phosphine complexes, readily available model catalysts are required. In this contribution, a comparative study of the hydrosilylation of aldehydes and ketones catalyzed by tris(trimethylphosphine) cobalt chloride, CoCl(PMe3)3 (1), and bis(silylene) cobalt chloride, Co(LSi:)2(PMe3)2Cl (2, LSi: = {PhC(NtBu)2}SiCl), is presented. It was found that both complexes 1 and 2 are good catalysts for the hydrosilylation of aldehydes and ketones under mild conditions. This catalytic system has a broad substrate scope and selectivity for multi-functional substrates. Silylene complex 2 shows higher activity than complex 1, bearing phosphine ligands, for aldehydes, but conversely, for ketones, the activity of complex 1 is higher than that of complex 2. It is worth noting that in the process of mechanistic studies the intermediates (PMe3)3Co(H)(Cl)(PhH2Si) (3) and (LSi:)2(PMe3)Co(H)(Cl)(PhH2Si) (4) were isolated from the stoichiometric reactions of 1 and 2 with phenylsilane, respectively. Further experiments confirmed that complex 3 is a real intermediate. A possible catalytic mechanism for the hydrosilylation of carbonyl compounds catalyzed by 1 was proposed based on the experimental investigation and literature reports, and this mechanism was further supported by DFT studies. The bis(silylene) complex 4 showed complicated behavior in solution. A series of experiments were designed to study the catalytic mechanism for the hydrosilylation of carbonyl compounds catalyzed by complex 2. According to the experimental results, the hydrosilylation of aldehydes catalyzed by 1 proceeds via a different mechanism than that of the analogous reaction with complex 2 as the catalyst. In the case of ketones, complex 4 is a real intermediate, indicating that both 1 and 2 catalyze the reaction by the same mechanism. The molecular structures of 3 and 4 were determined by single crystal X-ray diffraction analysis.
中文翻译：
亚甲硅基配体对钴膦配合物催化羰基氢化硅烷化性能的影响
为了研究亚甲硅基配体对钴膦配合物催化的羰基氢化硅烷化催化活性的影响，需要现成的模型催化剂。在这篇文章中，比较研究了三（三甲基膦）氯化钴 CoCl(PMe 3 ) 3 ( 1 ) 和双（甲硅基）氯化钴 Co(LSi:) 2 (PMe 3 ) 催化的醛和酮的氢化硅烷化) 2 Cl ( 2 , LSi: = {PhC(N t Bu) 2 }SiCl), 被提出。发现配合物1和2是温和条件下醛和酮的氢化硅烷化的良好催化剂。该催化体系具有广泛的底物范围和对多功能底物的选择性。亚甲硅基络合物2显示出比络合物1更高的活性，带有膦配体，对于醛，但相反，对于酮，络合物1的活性高于络合物2。值得注意的是，在机理研究过程中，中间体 (PMe 3 ) 3 Co(H)(Cl)(PhH 2 Si) ( 3 ) 和 (LSi:) 2 (PMe 3 )Co(H)(Cl) (PhH 2 Si) ( 4) 分别从1和2与苯基硅烷的化学计量反应中分离出来。进一步的实验证实复合物3是一个真正的中间体。基于实验研究和文献报道，提出了1催化羰基化合物氢化硅烷化的可能催化机理，并且 DFT 研究进一步支持了该机理。双（亚甲硅基）络合物4在溶液中表现出复杂的行为。设计了一系列实验来研究络合物2催化羰基化合物氢化硅烷化的催化机理。根据实验结果，醛催化的氢化硅烷化1通过与以配合物2作为催化剂的类似反应不同的机制进行。在酮的情况下，配合物4是一个真正的中间体，表明1和2通过相同的机制催化反应。通过单晶X射线衍射分析确定了3和4的分子结构。
更新日期：2023-04-18
中文翻译：
亚甲硅基配体对钴膦配合物催化羰基氢化硅烷化性能的影响
为了研究亚甲硅基配体对钴膦配合物催化的羰基氢化硅烷化催化活性的影响，需要现成的模型催化剂。在这篇文章中，比较研究了三（三甲基膦）氯化钴 CoCl(PMe 3 ) 3 ( 1 ) 和双（甲硅基）氯化钴 Co(LSi:) 2 (PMe 3 ) 催化的醛和酮的氢化硅烷化) 2 Cl ( 2 , LSi: = {PhC(N t Bu) 2 }SiCl), 被提出。发现配合物1和2是温和条件下醛和酮的氢化硅烷化的良好催化剂。该催化体系具有广泛的底物范围和对多功能底物的选择性。亚甲硅基络合物2显示出比络合物1更高的活性，带有膦配体，对于醛，但相反，对于酮，络合物1的活性高于络合物2。值得注意的是，在机理研究过程中，中间体 (PMe 3 ) 3 Co(H)(Cl)(PhH 2 Si) ( 3 ) 和 (LSi:) 2 (PMe 3 )Co(H)(Cl) (PhH 2 Si) ( 4) 分别从1和2与苯基硅烷的化学计量反应中分离出来。进一步的实验证实复合物3是一个真正的中间体。基于实验研究和文献报道，提出了1催化羰基化合物氢化硅烷化的可能催化机理，并且 DFT 研究进一步支持了该机理。双（亚甲硅基）络合物4在溶液中表现出复杂的行为。设计了一系列实验来研究络合物2催化羰基化合物氢化硅烷化的催化机理。根据实验结果，醛催化的氢化硅烷化1通过与以配合物2作为催化剂的类似反应不同的机制进行。在酮的情况下，配合物4是一个真正的中间体，表明1和2通过相同的机制催化反应。通过单晶X射线衍射分析确定了3和4的分子结构。
京公网安备 11010802027423号