Chromium(VI) Bisimido Dichloro, Bisimido Alkylidene, and Chromium(V) Bisimido Iodo N‐Heterocyclic Carbene Complexes

Reaction of CrCl2(N-tBu)2 with 1,3-dimethylimidazol-2-ylidene (IMe), 1,3-dimethyl-4,5-dichloroimidazol-2-ylidene (IMeCl2), 1,3-di(2-propyl)imidazol-2-ylidene (IPr), 1,3-dimesitylimidazol-2-ylidene (IMes) and 1,3-bis(2,6-(2-Pr)2C6H3)imidazol-2-ylidene (IDipp) yields the corresponding N-heterocyclic carbene (NHC) adducts CrCl2(IMe)(N-tBu)2 (1), CrCl2(IMeCl2)(N-tBu)2 (2), CrCl2(IPr)(N-tBu)2 (3), CrCl2(IMes)(N-tBu)2 (4) and CrCl2(IDipp)(N-tBu)2 (5). Likewise, reaction of CrCl2(N-2,6-(2-Pr)2C6H3)2 and CrCl2(N-adamantyl)2 with IMes yields CrCl2(N-2,6-(2-Pr)2C6H3)2(IMes) (6) and CrCl2(N-adamantyl)2(IMes) (7), respectively. Reaction of CrCl2(N-tBu)2 with the bidentate NHCs 1-R-3-(1-(2-LiO-C6H4))imidazol-2-ylidene yields the corresponding pentacoordinated Cr (VI) complexes CrCl2(1-R-3-(1-(2-O-C6H4))imidazol-2-ylidene)2C6H3)2(IMes) (R = 2,4,6-(CH3)3C6H2, 8), (R = tBu, 9), (R = 2-phenyl-C6H4, 10). Reaction of the chromium (VI) complex Cr(N-2,6-(2-Pr)2-C6H3)2(CH2C(CH3)3)2 with 1,3-dimethylimidazol-2-ylidene.AgI yields the bimetallic silver adduct of the chromium alkylidene complex (11) along with the tetrahedral chromium (V) complex CrI(N-2,6-(2-Pr)2-C6H3)2(1,3-dimethylimidazol-2-ylidene) (12). Compounds 1 – 4, 7, 9 – 12 were characterized by single crystal X-ray analysis. Finally, the chromium (VI) bisimido-amido complexes 13 – 14 bearing the N-6-(2-(diethylboryl)phenyl)pyridyl-2-yl-motif are reported. .All primary data files and processed data of the journal article from Buchmeiser group. Chromium(VI) Bisimido Dichloro, Bisimido Alkylidene, and Chromium(V) Bisimido Iodo N‐Heterocyclic Carbene Complexes

将二(叔丁基亚氨基)二氯化铬（CrCl₂(N-tBu)₂）分别与1,3-二甲基咪唑-2-亚基（1,3-dimethylimidazol-2-ylidene, IMe）、1,3-二甲基-4,5-二氯咪唑-2-亚基（1,3-dimethyl-4,5-dichloroimidazol-2-ylidene, IMeCl₂）、1,3-二(2-丙基)咪唑-2-亚基（1,3-di(2-propyl)imidazol-2-ylidene, IPr）、1,3-二均三甲苯基咪唑-2-亚基（1,3-dimesitylimidazol-2-ylidene, IMes）以及1,3-双(2,6-二(2-丙基)苯基)咪唑-2-亚基（1,3-bis(2,6-(2-Pr)₂C₆H₃)imidazol-2-ylidene, IDipp）反应，得到相应的氮杂环卡宾（N-heterocyclic carbene, NHC）加合物：CrCl₂(IMe)(N-tBu)₂（1）、CrCl₂(IMeCl₂)(N-tBu)₂（2）、CrCl₂(IPr)(N-tBu)₂（3）、CrCl₂(IMes)(N-tBu)₂（4）与CrCl₂(IDipp)(N-tBu)₂（5）。同理，二(2,6-二(2-丙基)苯基)二氯化铬（CrCl₂(N-2,6-(2-Pr)₂C₆H₃)₂）与二(金刚烷基基亚氨基)二氯化铬（CrCl₂(N-adamantyl)₂）分别与IMes反应，得到CrCl₂(N-2,6-(2-Pr)₂C₆H₃)₂(IMes)（6）与CrCl₂(N-adamantyl)₂(IMes)（7）。将CrCl₂(N-tBu)₂与双齿氮杂环卡宾1-R-3-(1-(2-锂氧基苯基))咪唑-2-亚基反应，得到相应的五配位铬(VI)配合物：CrCl₂(1-R-3-(1-(2-O-C₆H₄))imidazol-2-ylidene)₂(C₆H₃)₂(IMes)（R=2,4,6-三甲基苯基，8）、（R=叔丁基，9）、（R=2-苯基苯基，10）。将铬(VI)配合物Cr(N-2,6-(2-Pr)₂-C₆H₃)₂(CH₂C(CH₃)₃)₂与1,3-二甲基咪唑-2-亚基碘化银反应，得到亚烷基铬配合物的双金属银加合物（11），同时得到四面体构型的铬(V)配合物CrI(N-2,6-(2-Pr)₂-C₆H₃)₂(1,3-二甲基咪唑-2-亚基)（12）。化合物1–4、7、9–12通过单晶X射线衍射分析完成表征。最后，本文报道了带有N-6-(2-(二乙基硼基)苯基)吡啶-2-基骨架的铬(VI)双亚氨基-酰胺基配合物13–14。本研究所有原始数据与处理后数据均来自布赫迈泽（Buchmeiser）课题组的期刊文章，涉及的配合物类型为二氯双亚氨基铬(VI)、亚烷基双亚氨基铬(VI)及碘代双亚氨基铬(V)氮杂环卡宾配合物。