当前位置：
X-MOL 学术
›
Inorg. Chem. Front.
›
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.)
An electrochemically controlled release of NHCs using iron bis(dithiolene) N-heterocyclic carbene complexes
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-09-23 , DOI: 10.1039/d0qi00638f Jayaraman Selvakumar 1, 2, 3, 4 , Scott M. Simpson 1, 4, 5, 6 , Eva Zurek 1, 4, 7, 8 , Kuppuswamy Arumugam 1, 2, 3, 4
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-09-23 , DOI: 10.1039/d0qi00638f Jayaraman Selvakumar 1, 2, 3, 4 , Scott M. Simpson 1, 4, 5, 6 , Eva Zurek 1, 4, 7, 8 , Kuppuswamy Arumugam 1, 2, 3, 4
Affiliation
|
A series of five coordinated iron bis(dithiolene) complexes [Fe(NHC)(S2C2R2)2] (R = C6H5 or C6H4-p-OCH3) containing N-heterocyclic carbene (NHC) (NHC = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene or 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) were isolated in high yield (84–92%). The iron complexes were characterized by NMR spectroscopy and confirmed by single crystal X-ray diffraction studies. The combination of cyclic voltammetry and spectroelectrochemical analysis revealed that iron complexes undergo Fe–CNHC bond cleavage and release NHC upon subjection to electrochemical reduction. The electrochemically released NHC was trapped using 1-naphthylisothiocyanate and the adduct was isolated in nearly quantitative yield (∼99%). As a proof of concept, the electrochemically released NHC was subsequently used as a catalyst for synthesis of γ-butyrolactones from commercially available cinnamaldehydes.
中文翻译：
使用双（二硫代烯烃）N-杂环卡宾铁配合物电化学控制NHC的释放
含N杂环卡宾（R = C 6 H 5或C 6 H 4 - p -OCH 3）的一系列五个配位铁双（二硫代烯）配合物[Fe（NHC）（S 2 C 2 R 2）2 ]（R = C 6 H 5或C 6 H 4 - p -OCH 3） NHC）（NHC = 1,3-双（2,4,6-三甲基苯基）咪唑-2-亚基或1,3-双（2,4,6-三甲基苯基）-4,5-二氢咪唑-2-亚基）分离得率高（84–92％）。铁配合物通过NMR光谱表征，并通过单晶X射线衍射研究证实。循环伏安法和光谱电化学分析的结合表明，铁配合物经历了Fe–C NHC结合键裂解并在经受电化学还原后释放NHC。用1-萘基异硫氰酸酯捕获电化学释放的NHC，并以接近定量的收率（〜99％）分离加合物。作为概念证明，随后将电化学释放的NHC用作由市售肉桂醛合成γ-丁内酯的催化剂。
更新日期：2020-11-12
中文翻译：
使用双（二硫代烯烃）N-杂环卡宾铁配合物电化学控制NHC的释放
含N杂环卡宾（R = C 6 H 5或C 6 H 4 - p -OCH 3）的一系列五个配位铁双（二硫代烯）配合物[Fe（NHC）（S 2 C 2 R 2）2 ]（R = C 6 H 5或C 6 H 4 - p -OCH 3） NHC）（NHC = 1,3-双（2,4,6-三甲基苯基）咪唑-2-亚基或1,3-双（2,4,6-三甲基苯基）-4,5-二氢咪唑-2-亚基）分离得率高（84–92％）。铁配合物通过NMR光谱表征，并通过单晶X射线衍射研究证实。循环伏安法和光谱电化学分析的结合表明，铁配合物经历了Fe–C NHC结合键裂解并在经受电化学还原后释放NHC。用1-萘基异硫氰酸酯捕获电化学释放的NHC，并以接近定量的收率（〜99％）分离加合物。作为概念证明，随后将电化学释放的NHC用作由市售肉桂醛合成γ-丁内酯的催化剂。
京公网安备 11010802027423号