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Between imide, imidyl and nitrene – an imido iron complex in two oxidation states
Chemical Science ( IF 7.6 ) Pub Date : 2022-06-09 , DOI: 10.1039/d2sc01088g Sascha Reith 1 , Serhiy Demeshko 2 , Beatrice Battistella 3 , Alexander Reckziegel 1 , Christian Schneider 1 , Andreas Stoy 1 , Crispin Lichtenberg 1 , Franc Meyer 2 , Dominik Munz 4, 5 , C Gunnar Werncke 1
Chemical Science ( IF 7.6 ) Pub Date : 2022-06-09 , DOI: 10.1039/d2sc01088g Sascha Reith 1 , Serhiy Demeshko 2 , Beatrice Battistella 3 , Alexander Reckziegel 1 , Christian Schneider 1 , Andreas Stoy 1 , Crispin Lichtenberg 1 , Franc Meyer 2 , Dominik Munz 4, 5 , C Gunnar Werncke 1
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Imidyl and nitrene metal species play an important role in the N-functionalisation of unreactive C–H bonds as well as the aziridination of olefines. We report on the synthesis of the trigonal imido iron complexes [Fe(NMes)L2]0,− (L = –N{Dipp}SiMe3); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl) via reaction of mesityl azide (MesN3) with the linear iron precursors [FeL2]0,−. UV-vis-, EPR-, 57Fe Mössbauer spectroscopy, magnetometry, and computational methods suggest for the reduced form an electronic structure as a ferromagnetically coupled iron(II) imidyl radical, whereas oxidation leads to mixed iron(III) imidyl and electrophilic iron(II) nitrene character. Reactivity studies show that both complexes are capable of H atom abstraction from C–H bonds. Further, the reduced form [Fe(NMes)L2]− reacts nucleophilically with CS2 by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L2] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.
中文翻译：
亚胺、亚胺基和氮烯之间——两种氧化态的亚胺铁络合物
亚胺基和氮烯金属物质在非反应性 C-H 键的N官能化以及烯烃的氮丙啶化中起重要作用。我们报道了三角亚胺铁配合物[Fe(NMes)L 2 ] 0,- (L = –N{Dipp}SiMe 3 )的合成；Dipp = 2,6-二异丙基-苯基；Mes = (2,4,6-三甲基苯基) ，通过叠氮异三叉戟 (MesN 3 ) 与线性铁前体 [FeL 2 ] 0,-反应。UV-vis-、EPR-、57 Fe Mössbauer 光谱、磁力测量和计算方法表明，还原形式的电子结构为铁磁耦合铁（II) 亚胺基自由基，而氧化导致混合铁 ( III ) 亚胺基和亲电子铁 ( II ) 氮烯特性。反应性研究表明，这两种配合物都能够从 C-H 键中提取 H 原子。此外，还原形式[Fe(NMes)L 2 ] -通过插入亚氨基铁键与CS 2发生亲核反应，并在氮烯转移下与CO 发生亲电反应。中性的 [Fe(NMes)L 2 ] 配合物显示出增强的亲电行为，这可以通过氮烯转移到磷化氢来证明，但与整体反应性降低相结合。
更新日期：2022-06-09
中文翻译：
亚胺、亚胺基和氮烯之间——两种氧化态的亚胺铁络合物
亚胺基和氮烯金属物质在非反应性 C-H 键的N官能化以及烯烃的氮丙啶化中起重要作用。我们报道了三角亚胺铁配合物[Fe(NMes)L 2 ] 0,- (L = –N{Dipp}SiMe 3 )的合成；Dipp = 2,6-二异丙基-苯基；Mes = (2,4,6-三甲基苯基) ，通过叠氮异三叉戟 (MesN 3 ) 与线性铁前体 [FeL 2 ] 0,-反应。UV-vis-、EPR-、57 Fe Mössbauer 光谱、磁力测量和计算方法表明，还原形式的电子结构为铁磁耦合铁（II) 亚胺基自由基，而氧化导致混合铁 ( III ) 亚胺基和亲电子铁 ( II ) 氮烯特性。反应性研究表明，这两种配合物都能够从 C-H 键中提取 H 原子。此外，还原形式[Fe(NMes)L 2 ] -通过插入亚氨基铁键与CS 2发生亲核反应，并在氮烯转移下与CO 发生亲电反应。中性的 [Fe(NMes)L 2 ] 配合物显示出增强的亲电行为，这可以通过氮烯转移到磷化氢来证明，但与整体反应性降低相结合。
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