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Ruthenium-Hydride Assisted Remarkable Diversity Towards Non-Spectator Feature of Benzodifuroxan.
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2020-08-11 , DOI: 10.1002/asia.202000849
Sanchaita Dey 1 , Sanjib Panda 1 , Goutam Kumar Lahiri 1
Affiliation  

The present article demonstrates that ruthenium‐hydride [RuII(H)(Cl)(CO)(PPh3)3] mediated diverse functionalization modes of benzodifuroxan (BDF) encompassing two furoxan rings. Hydride transfer from the metal precursor facilitated multiple cascade reactions involving unsymmetrical cleavage of the furoxan rings of BDF, leading to the one‐pot formation of a series of ruthenium (II) coordinated functionalized ligands exhibiting bidentate κ2‐N,O, κ2‐N,N′ and bis‐bidentate μ‐bis(κ2‐N,O) modes. Further, a moderately stable intermediate species was also encountered in the reaction sequence in which the transformed deoxygenated ligand coordinated to the metal ion via the rarely manifested furazan ring (κ2‐N,N′′ mode). The products were authenticated by their single‐crystal X‐ray structures and other spectroscopic/analytical techniques. Redox non‐innocence of the functionalized ligands in the complexes was illustrated by spectroelectrochemistry (cyclic voltammmetry, UV‐Vis. and EPR) in conjunction with DFT/TD‐DFT calculations. Mechanistic outline for the facile ring opening processes of BDF including interconversions of complexes (e. g. reductive ring opening) were also addressed.

中文翻译:

氢化钌辅助苯并呋喃恶烷具有非观片特性。

本文证明了氢化钌[Ru II(H)(Cl)(CO)(PPh 33 ]介导了涵盖两个呋喃环的苯并二呋喃(BDF)的多种功能化模式。从金属前体氢化物转移促进涉及BDF的氧化呋咱环的不对称裂解多个级联反应,导致一锅煮形成一系列的钌(II)的配位配位体官能化表现出双齿κ 2 -N,O,κ 2 - N,N'和双-二齿μ双(κ 2‐N,O)模式。此外,适度稳定的中间物质在其中转化脱氧配体经由很少表现呋咱环配位到金属离子(κ的反应序列,也遇到2 -N,N''模式)。产品通过其单晶X射线结构和其他光谱/分析技术进行了鉴定。配合物的光谱电化学(循环伏安法,UV-Vis。和EPR)结合DFT / TD-DFT计算说明了配合物中功能化配体的氧化还原无毒。还讨论了BDF的容易的开环过程的机理,包括络合物的相互转化(例如还原性开环)。
更新日期:2020-10-17
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