硼桥联三氮杂环卡宾配位的铁分子氮配合物:合成、表征和反应性质研究

doi:10.6023/A18030095

化学学报 ›› 2018, Vol. 76 ›› Issue (6): 445-452.DOI: 10.6023/A18030095 上一篇下一篇

研究论文

硼桥联三氮杂环卡宾配位的铁分子氮配合物:合成、表征和反应性质研究

凡一明^a, 程骏^b, 高亚飞^b, 施敏^a,b, 邓亮^b

a 华东理工大学化学与分子工程学院结构可控先进功能材料及其制备教育部重点实验室上海 200237;
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室分子合成科学卓越中心上海 200032

投稿日期:2018-03-10 发布日期:2018-04-08
通讯作者: 施敏,E-mail:mshi@mail.sioc.ac.cn;邓亮,E-mail:deng@sioc.ac.cn E-mail:mshi@mail.sioc.ac.cn;deng@sioc.ac.cn
基金资助:
项目受科技部国家重点研发计划（No.2016YFA0202900）、国家自然科学基金（Nos.21725104，21690062和21432001）、中科院战略先导科技专项（No.XDB20000000）和中央高校基本科研业务费专项资金（No.222201717003）资助.

Iron Dinitrogen Complexes Supported by Tris(NHC)borate Ligand: Synthesis, Characterization, and Reactivity Study

Fan Yiming^a, Cheng Jun^b, Gao Yafei^b, Shi Min^a,b, Deng Liang^b

a School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237;
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2018-03-10 Published:2018-04-08
Contact: 10.6023/A18030095 E-mail:mshi@mail.sioc.ac.cn;deng@sioc.ac.cn
Supported by:
Project supported by the National Key Research and Development Program (No. 2016YFA0202900), the National Natural Science Foundation of China (Nos. 21725104, 21690062, 21432001), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000) and the Fundamental Research Funds for the Central Universities (No. 222201717003).

文章分享

1. 硼桥联三氮杂环卡宾配位的铁分子氮配合物:合成、表征和反应性质研究.PDF(1542KB)

摘要/Abstract

研究了氮上取代基为1-金刚烷基的苯基硼桥联三氮杂环卡宾配体在铁促进的氮气活化转化反应中的应用.通过苯基硼桥联三氮杂环卡宾亚铁氯化物[PhB（AdIm）₃FeCl]（1）在氮气氛下与KC₈反应合成了一价铁分子氮配合物[PhB（AdIm）₃Fe（N₂）]（2）.进一步通过2与KC₈和18-C-6的反应合成了零价铁分子氮配合物[K（18-C-6）（THF）]-[PhB（AdIm）₃Fe（N₂）]（4）.这些配合物均通过核磁共振、紫外吸收光谱、红外光谱、元素分析等表征，其中配合物2和4的结构经单晶X射线衍射表征确定.配合物2和4的N—N伸缩振动频率分别为1928和1807 cm^－1，均为同价态铁末端分子氮配合物最低值.在过量KC₈和Me₃SiCl存在下，配合物1，2和4均可催化N₂的还原硅基化反应，生成N（SiMe₃）₃.催化体系的TON可达87.

关键词: 氮杂环卡宾, 铁, 分子氮配合物, 氮气活化, 氮气硅基化

The use of the N-adamantyl-substituted tris(NHC)borate ligand phenyltris(3-(1-adamantylimidazol-2-ylidene))borate (PhB(AdIm)₃^-) has enabled the preparation of the high-spin tetrahedral iron(I)-and iron(0)-N₂ complexes[PhB(AdIm)₃Fe(N₂)] (2) and[K(18-C-6)(THF)] [PhB(AdIm)₃Fe(N₂)] (4), from the reduction of the ferrous precursor[PhB(AdIm)₃FeCl] (1) and the iron(I) complex 2 with KC₈ under N₂, respectively. Single-crystal X-ray diffraction studies revealed a distorted tetrahedral coordination geometry for the iron centers in 2 and 4 with the terminally bonded N₂ ligand sitting in the cavity composed by the three adamantyl groups of the borate ligand. The frequencies of the N-N stretching resonance (1928 and 1807 cm^-1) of 2 and 4 are the lowest among the reported terminal N₂complexes of iron(I) and iron(0), respectively. ⁵⁷Fe Mössbauer spectrum (δ=0.59 mms^-1; ΔE_Q=1.31 mms^-1) and solution magnetic susceptibility measurement (μ_eff=5.2(1) μ_B) of 2 supported its high-spin iron(I) nature. The cyclic voltammogram of 2 measured in THF shows a quasi-reversible redox waves with E_1/2=-2.11 V (vs SCE), which is assignable to the corresponding redox process of[PhB(AdIm)₃Fe(N₂)]^1-/0. In addition, the reaction of 2 with an excess amount of CO led to the formation of the bis(carbonyl)iron(I) complex,[PhB(AdIm)₃Fe(CO)₂] (3), that was characterized by IR spectrum, solution magnetic susceptibility measurement, ¹H NMR, as well as elemental analysis. The protonation of 2 and 4 with HCl or HOTf at -78℃ only led to the formation of NH₂NH₂ and NH₃ in low yields[less than 9(3)% and 5(3)% (per mol Fe), respectively]. However, 1, 2, and 4 proved effective catalysts for the reductive silylation of N₂by KC₈ and Me₃SiCl to afford N(SiMe₃)₃ with comparable catalytic activity. The TON of these catalytic systems could reach 87 using 0.005 mmol of the catalyst, 2000 equiv. of KC₈, and 2000 equiv. of Me₃SiCl in 10 mL Et₂O at room temperature after 24 h.

Key words: N-heterocyclic carbene, iron, dinitrogencomplex, N₂ activation, reductive silylation of N₂

引用此文

凡一明, 程骏, 高亚飞, 施敏, 邓亮. 硼桥联三氮杂环卡宾配位的铁分子氮配合物:合成、表征和反应性质研究[J]. 化学学报, 2018, 76(6): 445-452.

Fan Yiming, Cheng Jun, Gao Yafei, Shi Min, Deng Liang. Iron Dinitrogen Complexes Supported by Tris(NHC)borate Ligand: Synthesis, Characterization, and Reactivity Study[J]. Acta Chim. Sinica, 2018, 76(6): 445-452.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] (a) Winter, H. C.; Burris, R. H. Annu. Rev. Biochem. 1976, 45, 409.
(b) Bulen, W. A.; LeComte, J. R. Proc. Natl. Acad. Sci. U. S. A. 1966, 56, 979.
(c) Mortenson, L. E. Fed. Proc. 1965, 24, 233.
(d) Mortenson, L. E. Biochim. Biophys. Acta 1966, 127, 18.
(e) Hageman, R. V.; Burris, R. H. Proc. Natl. Acad. Sci. U. S. A. 1978, 75, 2699.
(f) Dean, D. R.; Bolin, J. T.; Zheng, L. J. Bacteriol. 1993, 175, 6737.
(g) Howard, J. B.; Rees, D. C. Annu. Rev. Biochem. 1994, 63, 235.
(h) Kim, J.; Rees, D. C. Biochemistry 1994, 33, 389.
(i) Wang, Y.-S.; Li, J.-L. Prog. Nat. Sci. 2000, 10, 481. (王友绍, 李季伦, 自然科学进展, 2000, 10, 481.)
[2] (a) Spatzal, T.; Aksoyoglu, M.; Zhang, L.; Andrade, S. L. A.; Schleicher, E.; Weber, S.; Rees, D. C.; Einsle, O. Science 2011, 334, 940.
(b) Lancaster, K. M.; Roemelt, M.; Ettenhuber, P.; Hu, Y.; Ribbe, M. W.; Neese, F.; Bergmann, U.; DeBeer, S. Science 2011, 334, 974.
(c) Lancaster, K. M.; Hu, Y.; Bergmann, U.; Ribbe, M. W.; DeBeer, S. J. Am. Chem. Soc. 2013, 135, 610.
(d) Wiig, J. A.; Hu, Y.; Lee, C. C.; Ribbe, M. W. Science 2012, 337, 1672.
(e) Wiig, J. A.; Lee, C. C.; Hu, Y.; Ribbe, M. W. J. Am. Chem. Soc. 2013, 135, 4982.
(f) Zhang, C.-X.; Fan, H.-J.; Liu, Q.-T. Prog. Chem. 1997, 9, 266. (张纯喜, 樊红军, 刘秋田, 化学进展, 1997, 9, 266.)
(g) Chen, Q.-L.; Chen, H.-B.; Cao, Z.-X.; Zhou, Z.-H.; Wan, H.-L.; Li, Y.; Li, J.-L. Sci. China, Chem. 2014, 44, 1849. (陈全亮, 陈洪斌, 曹泽星, 周朝晖, 万惠霖, 李颖, 李季伦, 中国科学:化学, 2014, 44, 1849.)
[3] (a) Hoffman, B. M.; Lukoyanov, D.; Yang, Z.-Y.; Dean, D. R.; Seefeldt, L. C. Chem. Rev. 2014, 114, 4041.
(b) Coric, I.; Holland, P. L. J. Am. Chem. Soc. 2016, 138, 7200.
[4] (a) Rittle, J.; Peters, J. C. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 15898.
(b) Creutz, S. E.; Peters, J. C. J. Am. Chem. Soc. 2014, 136, 1105.
(c) Coric, I.; Mercado, B. Q.; Bill, E.; Vinyard, D. J.; Holland, P. L. Nature 2015, 526, 96.
(d) Ung, G.; Peters, J. C. Angew. Chem., Int. Ed. 2015, 54, 532.
(e) Ouyang, Z.-W.; Cheng, J.; Li, L.-L.; Bao, X.-L.; Deng, L. Chem.-Eur. J. 2016, 22, 14162.
[5] (a) Kastner, J.; Bl?chl, P. E. J. Am. Chem. Soc. 2007, 129, 2998.
(b) Spatzal, T.; Perez, K. A.; Einsle, O.; Howard, J. B.; Rees, D. C. Science 2014, 345, 1620.
[6] (a) Hazari, N. Chem. Soc. Rev. 2010, 39, 4044.
(b) Crossland, J. L.; Tyler, D. R. Coord. Chem. Rev. 2010, 254, 1883.
(c) Ohki, Y.; Seino, H. Dalton Trans. 2016, 45, 874.
(d) Danopoulos, A. A.; Wright, J. A.; Motherwell, W. B. Chem. Commun. 2005, 784.
(e) Pugh, D.; Wells, N. J.; Evans, D. J.; Danopoulos, A. A. Dalton Trans. 2009, 7189.
(f) Yu, R. P.; Darmon, J. M.; Hoyt, J. M.; Margulieux, G. W.; Turner, Z. R.; Chirik, P. J. ACS Catal. 2012, 2, 1760.
(g) Bartholomew, E. R.; Volpe, E. C.; Wolczanski, P. T.; Lobkovsky, E. B.; Cundari, T. R. J. Am. Chem. Soc. 2013, 135, 3511.
[7] (a) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39.
(b) Glorius, F., N-Heterocyclic Carbenes in Transition Metal Catalysis, Topics in Organometallic Chemistry, Vol. 21, Springer, Berlin, 2007.
(c) Hahn, F. E.; Jahnke, M. C. Angew. Chem., Int. Ed. 2008, 47, 3122.
[8] (a) Ingleson, M. J.; Layfield, R. A. Chem. Commun. 2012, 48, 3579.
(b) Riener, K.; Haslinger, S.; Raba, A.; H??gerl, M. P.; Cokoja, M.; Herrmann, W. A.; Kühn, F. E. Chem. Rev. 2014, 114, 5215.
[9] McSkimming, A.; Harman, W. H. J. Am. Chem. Soc. 2015, 137, 8940.
[10] Cowley, R. E.; Bontchev, R. P.; Duesler, E. N.; Smith, J. M. Inorg. Chem. 2006, 45, 9771.
[11] Scepaniak, J. J.; Fulton, M. D.; Bontchev, R. P.; Duesler, E. N.; Kirk, M. L.; Smith, J. M. J. Am. Chem. Soc. 2008, 130, 10515.
[12] (a) Ouyang, Z.-W.; Meng, Y.; Cheng, J.; Xiao, J.; Gao, S.; Deng, L. Organometallics 2016, 35, 1361.
(b) Ohki, Y.; Hoshino, R.; Tatsumi, K. Organometallics 2016, 35, 1368.
[13] Mankad, N. P.; Whited, M. T.; Peters, J. C. Angew. Chem., Int. Ed. 2007, 46, 5768.
[14] Gilbert-Wilson, R.; Field, L. D.; Colbran, S. B.; Bhadbhade, M. M. Inorg. Chem. 2013, 52, 3043.
[15] Hounjet, L. J.; Adhikari, D.; Pink, M.; Carroll, P. J.; Mindiola, D. J. Z. Anorg. Allg. Chem. 2015, 641, 45.
[16] Smith, J. M. Comments Inorg. Chem. 2008, 29, 189.
[17] Hickey, A. K.; Chen, C.; Pink, M.; Smith, J. M. Organometallics 2015, 34, 4560.
[18] Lee, Y.; Mankad, N. P.; Peters, J. C. Nat. Chem. 2010, 2, 558.
[19] Komiya, S.; Akita, M.; Yoza, A.; Kasuga, N.; Fukuoka, A.; Kai, Y. J. Chem. Soc., Chem. Commun. 1993, 787.
[20] Gilbert-Wilson, R.; Field, L. D.; Colbran, S. B.; Bhadbhade, M. M. Inorg. Chem. 2013, 52, 3043.
[21] Creutz, S. E.; Peters, J. C. J. Am. Chem. Soc. 2014, 136, 1105.
[22] (a) Hills, A.; Hughes, D. A.; Jimenez-Tenorio, M.; Leigh, G. J.; Rowley, A. T. J. Chem. Soc., Dalton Trans. 1993, 3041.
(b) Hall, D. A.; Leigh, G. J. J. Chem. Soc., Dalton Trans. 1996, 3539.
[23] Gilbertson, J. D.; Szymczak, N. K.; Tyler, D. R. J. Am. Chem. Soc. 2005, 127, 10184.
[24] George, T. A.; Rose, D. J.; Chang, Y.; Chen, Q.; Zubieta, J. Inorg. Chem. 1995, 34, 1295.
[25] Li, J.-P.; Yin, J.-H.; Yu, C.; Zhang, W.-X.; Xi, Z.-F. Acta Chim. Sinica 2017, 75, 733. (李嘉鹏, 殷剑昊, 俞超, 张文雄, 席振峰, 化学学报, 2017, 75, 733.)
[26] Shiina, K. J. Am. Chem. Soc. 1972, 94, 9266.
[27] Tanaka, H.; Sasada, A.; Kouno, T.; Yuki, M.; Miyake, Y.; Nakanishi, H.; Nishibayashi, Y.; Yoshizawa, K. J. Am. Chem. Soc. 2011, 133, 3498.
[28] Liao, Q.; Saffon-Merceron, N.; Mezailles, N. Angew. Chem., Int. Ed. 2014, 53, 14206.
[29] Araake, R.; Sakadani, K.; Tada, M.; Sakai, Y.; Ohki, Y. J. Am. Chem. Soc. 2017, 139, 5596.
[30] Siedschlag, R. B.; Bernales, V.; Vogiatzis, K. D.; Planas, N.; Clouston, L. J.; Bill, E.; Gagliardi, L.; Lu, C. C. J. Am. Chem. Soc. 2015, 137, 4638.
[31] Gao, Y.-F.; Li, G.-Y.; Deng, L. J. Am. Chem. Soc. 2018, 140, 2239.
[32] Weatherburu, M. W. Anal. Chem. 1967, 39, 971.
[33] Watt, G. W.; Chrisp, J. D. Anal. Chem. 1952, 24, 2006.

硼桥联三氮杂环卡宾配位的铁分子氮配合物:合成、表征和反应性质研究

Iron Dinitrogen Complexes Supported by Tris(NHC)borate Ligand: Synthesis, Characterization, and Reactivity Study

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	徐豪杰, 韩世国, 孙志华, 罗军华. 二维有机-无机杂化钙钛矿铁电材料的研究进展[J]. 化学学报, 2021, 79(1): 23-35.
[2]	白云平, 崔春明. 硅卡宾铁(0)氮气配合物催化的炔烃选择性硼氢化反应[J]. 化学学报, 2020, 78(8): 763-766.
[3]	张静, 汤功奥, 曾誉, 王保兴, 刘力玮, 吴强, 杨立军, 王喜章, 胡征. 可溶性氧化-还原介质促进分级结构碳纳米笼的锂氧电池性能[J]. 化学学报, 2020, 78(6): 572-576.
[4]	刘静, 顾天航, 王伟, 刘爱荣, 张伟贤. 纳米零价铁在水相反应中的表面化学和晶相转化[J]. 化学学报, 2019, 77(2): 121-129.
[5]	杨波, 张永丽. 非均相芬顿体系协同去除复合双污染物: 化学转化, pH影响和机理分析[J]. 化学学报, 2019, 77(10): 1017-1023.
[6]	王艺霖, 王敏杰, 李静, 魏子栋. 铁镍合金纳米颗粒镶嵌的多级孔氮掺杂碳催化剂的制备及析氧性能研究[J]. 化学学报, 2019, 77(1): 84-89.
[7]	安伦, 童非非, 张新刚. 铁催化下二芳基锌和芳基格氏试剂的二氟烷基化反应[J]. 化学学报, 2018, 76(12): 977-982.
[8]	王乐明, 王骞, 陈杰安, 黄湧. Lewis酸对氮杂环卡宾协同催化体系中反应途径的调控[J]. 化学学报, 2018, 76(11): 850-856.
[9]	鲁鸿, 刘金宇, 李红玉, 许鹏飞. 氮杂环卡宾与过渡金属共催化反应研究进展[J]. 化学学报, 2018, 76(11): 831-837.
[10]	黄丹维, 何佳, 谷亚威, 何锋. 球磨微米硫化零价铁活化双氧水降解有机污染物的研究[J]. 化学学报, 2017, 75(9): 866-872.
[11]	李嘉鹏, 殷剑昊, 俞超, 张文雄, 席振峰. 从氮气直接合成含氮有机化合物[J]. 化学学报, 2017, 75(8): 733-743.
[12]	陈海军, 黄舒怡,张志宾, 刘云海, 王祥科. 功能性纳米零价铁的构筑及其对环境放射性核素铀的富集应用研究进展[J]. 化学学报, 2017, 75(6): 560-574.
[13]	易云强, 吴娟, 方战强. 天然有机质在生物炭负载纳米镍铁降解十溴联苯醚过程中的影响作用机理辨识[J]. 化学学报, 2017, 75(6): 629-636.
[14]	汤晶, 汤琳, 冯浩朋, 董浩然,章毅, 刘思诗, 曾光明. 硫化纳米零价铁去除水体污染物的研究进展[J]. 化学学报, 2017, 75(6): 575-582.
[15]	穆毅, 贾法龙, 艾智慧, 张礼知. 纳米零价铁活化分子氧原理及降解有机污染物性能增强策略[J]. 化学学报, 2017, 75(6): 538-543.