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Pyridine N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-06-19 , DOI: 10.1039/d0dt00392a
Guoliang Chang 1 , Peng Zhang 1 , Wenjing Yang 1 , Shangqing Xie 1 , Hongjian Sun 1 , Xiaoyan Li 1 , Olaf Fuhr 2 , Dieter Fenske 2
Affiliation  

Five [PSiP]-pincer iron hydrides 1–5, [(2-Ph2PC6H4)2HSiFe(H)(PMe3)2 (1), (2-Ph2PC6H4)2MeSiFe(H)(PMe3)2 (2), (2-Ph2PC6H4)2PhSiFe(H)(PMe3)2 (3), (2-(iPr)2PC6H4)2HSiFe(H)(PMe3) (4), and (2-(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (5)], were used as catalysts to study the effects of pyridine N-oxide and the electronic properties of [PSiP]-ligands on the catalytic hydrosilylation of carbonyl compounds. It was proved for the first time that this catalytic process could be promoted with pyridine N-oxide as the initiator at 30 °C because the addition of pyridine N-oxide is beneficial for the formation of an unsaturated hydrido iron complex, which is the key intermediate in the catalytic mechanism. Complex 4 as the best catalyst shows excellent catalytic performance. Among the five complexes, complex 3 was new and the molecular structure of complex 3 was determined by single crystal X-ray diffraction. A proposed mechanism was discussed.

中文翻译:

吡啶N-氧化物促进了[PSiP]-钳制铁氢化物催化的羰基化合物的氢化硅烷化。

五个[PSiP]钳制铁氢化物1-5,[(2-Ph 2 PC 6 H 42 HSiFe(H)(PMe 321),(2-Ph 2 PC 6 H 42 MeSiFe( H)(PMe 322),(2-Ph 2 PC 6 H 42 PhSiFe(H)(PMe 323),(2-(iPr)2 PC 6 H 42 HSiFe(高)(PMe3)( 4)和(2-(iPr) 2 PC 6 H 4 2 MeSiFe(H)(PMe 3 2 5)]用作催化剂,研究吡啶-N-氧化物和电子[PSiP]-配体对羰基化合物催化氢化硅烷化反应的影响 首次证明在30°C下以吡啶N-氧化物为引发剂可以促进该催化过程,因为添加吡啶N-氧化物有利于形成不饱和氢化铁络合物,这是关键催化机制中的中间体。复杂4作为最好的催化剂表现出优异的催化性能。在五个复合物,复合物3是新的,复杂的分子结构3通过单晶X射线衍射来确定。讨论了一种建议的机制。
更新日期:2020-07-17
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