Three-Coordinate Iron(IV) Bisimido Complexes with Aminocarbene Ligation: Synthesis, Structure, and Reactivity
文献类型：期刊论文
| 作者 | Wang, Lei1; Hu, Lianrui2; Zhang, Hezhong1; Chen, Hui2; Deng, Liang1 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2015-11-11 |
| 卷号 | 137期号:44页码:14196-14207 |
| 英文摘要 | High-valent iron imido species are implicated as reactive intermediates in many iron-catalyzed transformations. However, isolable complexes of this type are rare, and their reactivity is poorly understood. Herein, we report the synthesis, characterization, and reactivity studies on novel three-coordinate iron(IV) bisimido complexes with aminocarbene ligation. Using our recently reported synthetic method for [LFe(NDipp)(2)] (L = IMes, 1; Me-2-cAAC, 2), four new iron(IV) imido complexes, RIPr)Fe(NDipp)(2)] (3) and [(Me-2-cAAC)Fe(NR)(2)] (R = Mes, 4; Ad, 5; CMe2CH2Ph, 6), were prepared from the reactions of three-coordinate iron(0) compounds with organic azides. Characterization data acquired from H-1 and C-13 NMR spectroscopy, Fe-57 Mossbauer spectroscopy, and X-ray diffraction studies suggest a low-spin singlet ground state for these iron(IV) complexes and the multiple-bond character of their Fe-N bonds. A reactivity study taking the reactions of 1 as representative. revealed an intramolecular alkane dehydrogenation of 1 to produce the iron(II) complex [(IMes)Fe(NHDipp) (NHC6H3-2-Pr-i-6-CMe=CH2)] (7), a Si-H bond activation reaction of 1 with PhSiH3 to produce the iron(II) complex [(IMes)Fe(NHDipp)(NDippSiPhH(2))] (8), and a [2+2]-addition reaction of 1 with PhNCNPh and p-Pr'C6H4NCO to form the corresponding open-shell formal iron(IV) monoimido complexes [(IMes)Fe(NDipp)(N(Dipp)C(NPh)(=NPh))] (9) and [(IMes)Fe(NDipp)(N(Dipp)C(O)N(p-(PrC6H4)-C-i))] (10), as well as [NDipp]-group-transfer reactions with CO and (BuNC)-N-t. Density functional theory calculations suggested that the alkane chain dehydrogenation reaction starts with a hydrogen atom abstraction mechanism, whereas the Si-H activation reaction proceeds in a [2 pi-2 sigma]-addition manner. Both reactions have the pathways at the triplet potential energy surfaces being energetically preferred, and have formal iron(IV) hydride and iron(IV) silyl species as intermediates, respectively. The low-coordinate nature and low d-electron count (d(4)) of iron(IV) imido complexes are thought to be the key features endowing their unique reactivity. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/29252]  |
| 专题 | 化学研究所_光化学实验室 |
| 作者单位 | 1.Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China 2.Chinese Acad Sci, Inst Chem, CAS Key Lab Photochem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang, Lei,Hu, Lianrui,Zhang, Hezhong,et al. Three-Coordinate Iron(IV) Bisimido Complexes with Aminocarbene Ligation: Synthesis, Structure, and Reactivity[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(44):14196-14207. |
| APA | Wang, Lei,Hu, Lianrui,Zhang, Hezhong,Chen, Hui,&Deng, Liang.(2015).Three-Coordinate Iron(IV) Bisimido Complexes with Aminocarbene Ligation: Synthesis, Structure, and Reactivity.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,137(44),14196-14207. |
| MLA | Wang, Lei,et al."Three-Coordinate Iron(IV) Bisimido Complexes with Aminocarbene Ligation: Synthesis, Structure, and Reactivity".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137.44(2015):14196-14207. |
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来源：化学研究所
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