Citation: 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 Chimica Sinica, ;2018, 76(6): 445-452. doi: 10.6023/A18030095 shu

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

Corresponding author: Shi Min, mshi@mail.sioc.ac.cn Deng Liang, deng@sioc.ac.cn
Received Date: 10 March 2018
Available Online: 4 June 2018
Fund Project: the National Natural Science Foundation of China 21690062the National Key Research and Development Program 2016YFA0202900the National Natural Science Foundation of China 21725104the Strategic Priority Research Program of the Chinese Academy of Sciences XDB20000000the National Natural Science Foundation of China 21432001Project 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)the Fundamental Research Funds for the Central Universities 222201717003

Figures(6)

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.
- N-heterocyclic carbene,
- iron,
- dinitrogencomplex,
- N₂ activation,
- reductive silylation of N₂
1. [1]
2. [2]
3. [3]
  (a) Hoffman, B. M. ; Lukoyanov, D. ; Yang, Z. -Y. ; Dean, D. R. ; Seefeldt, L. C. Chem. Rev. 2014, 114, 4041. (b) Čorić, I. ; Holland, P. L. J. Am. Chem. Soc. 2016, 138, 7200.
4. [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) Čorić, 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. [5]
  (a) Kästner, J. ; Blöchl, 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. [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. [7]
  (a) Bourissou, D. ; Guerret, O. ; Gabbaï, 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. [8]
  (a) Ingleson, M. J. ; Layfield, R. A. Chem. Commun. 2012, 48, 3579. (b) Riener, K. ; Haslinger, S. ; Raba, A. ; Högerl, M. P. ; Cokoja, M. ; Herrmann, W. A. ; Kühn, F. E. Chem. Rev. 2014, 114, 5215.
9. [9]
  McSkimming, A.; Harman, W. H. J. Am. Chem. Soc. 2015, 137, 8940. doi: 10.1021/jacs.5b06337
10. [10]
  Cowley, R. E.; Bontchev, R. P.; Duesler, E. N.; Smith, J. M. Inorg. Chem. 2006, 45, 9771. doi: 10.1021/ic061299a
11. [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. doi: 10.1021/ja8027372
12. [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. [13]
  Mankad, N. P.; Whited, M. T.; Peters, J. C. Angew. Chem., Int. Ed. 2007, 46, 5768. doi: 10.1002/(ISSN)1521-3773
14. [14]
  Gilbert-Wilson, R.; Field, L. D.; Colbran, S. B.; Bhadbhade, M. M. Inorg. Chem. 2013, 52, 3043. doi: 10.1021/ic3024953
15. [15]
  Hounjet, L. J.; Adhikari, D.; Pink, M.; Carroll, P. J.; Mindiola, D. J. Z. Anorg. Allg. Chem. 2015, 641, 45. doi: 10.1002/zaac.201400173
16. [16]
  Smith, J. M. Comments Inorg. Chem. 2008, 29, 189. doi: 10.1080/02603590802590080
17. [17]
  Hickey, A. K.; Chen, C.; Pink, M.; Smith, J. M. Organometallics 2015, 34, 4560. doi: 10.1021/acs.organomet.5b00646
18. [18]
  Lee, Y.; Mankad, N. P.; Peters, J. C. Nat. Chem. 2010, 2, 558. doi: 10.1038/nchem.660
19. [19]
  Komiya, S.; Akita, M.; Yoza, A.; Kasuga, N.; Fukuoka, A.; Kai, Y. J. Chem. Soc., Chem. Commun. 1993, 787.
20. [20]
  Gilbert-Wilson, R.; Field, L. D.; Colbran, S. B.; Bhadbhade, M. M. Inorg. Chem. 2013, 52, 3043. doi: 10.1021/ic3024953
21. [21]
  Creutz, S. E.; Peters, J. C. J. Am. Chem. Soc. 2014, 136, 1105. doi: 10.1021/ja4114962
22. [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. [23]
  Gilbertson, J. D.; Szymczak, N. K.; Tyler, D. R. J. Am. Chem. Soc. 2005, 127, 10184. doi: 10.1021/ja053030g
24. [24]
  George, T. A.; Rose, D. J.; Chang, Y.; Chen, Q.; Zubieta, J. Inorg. Chem. 1995, 34, 1295. doi: 10.1021/ic00109a046
25. [25]
  Li, J.-P.; Yin, J.-H.; Yu, C.; Zhang, W.-X.; Xi, Z.-F. Acta Chim. Sinica 2017, 75, 733.
26. [26]
  Shiina, K. J. Am. Chem. Soc. 1972, 94, 9266. doi: 10.1021/ja00781a068
27. [27]
  Tanaka, H.; Sasada, A.; Kouno, T.; Yuki, M.; Miyake, Y.; Nakanishi, H.; Nishibayashi, Y.; Yoshizawa, K. J. Am. Chem. Soc. 2011, 133, 3498. doi: 10.1021/ja109181n
28. [28]
  Liao, Q.; Saffon-Merceron, N.; Mezailles, N. Angew. Chem., Int. Ed. 2014, 53, 14206. doi: 10.1002/anie.v53.51
29. [29]
  Araake, R.; Sakadani, K.; Tada, M.; Sakai, Y.; Ohki, Y. J. Am. Chem. Soc. 2017, 139, 5596. doi: 10.1021/jacs.7b01965
30. [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. doi: 10.1021/jacs.5b01445
31. [31]
  Gao, Y.-F.; Li, G.-Y.; Deng, L. J. Am. Chem. Soc. 2018, 140, 2239. doi: 10.1021/jacs.7b11660
32. [32]
  Weatherburu, M. W. Anal. Chem. 1967, 39, 971. doi: 10.1021/ac60252a045
33. [33]
  Watt, G. W.; Chrisp, J. D. Anal. Chem. 1952, 24, 2006. doi: 10.1021/ac60072a044
1. [1]
  Hong RAO , Yang HU , Yicong MA , Chunxin LÜ , Wei ZHONG , Lihua DU . Synthesis and in vitro anticancer activity of phenanthroline-functionalized nitrogen heterocyclic carbene homo- and heterobimetallic silver/gold complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2429-2437. doi: 10.11862/CJIC.20240275
2. [2]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
3. [3]
  Qingjun PAN , Zhongliang GONG , Yuwu ZHONG . Advances in modulation of the excited states of photofunctional iron complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 45-58. doi: 10.11862/CJIC.20240365
4. [4]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
5. [5]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
6. [6]
  Jinfeng Chu , Yicheng Wang , Ji Qi , Yulin Liu , Yan Li , Lan Jin , Lei He , Yufei Song . Comprehensive Chemical Experiment Design: Convenient Preparation and Characterization of an Oxygen-Bridged Trinuclear Iron(III) Complex. University Chemistry, 2024, 39(7): 299-306. doi: 10.3866/PKU.DXHX202310105
7. [7]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
8. [8]
  Yuanpei ZHANG , Jiahong WANG , Jinming HUANG , Zhi HU . Preparation of magnetic mesoporous carbon loaded nano zero-valent iron for removal of Cr(Ⅲ) organic complexes from high-salt wastewater. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1731-1742. doi: 10.11862/CJIC.20240077
9. [9]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-. doi: 10.3866/PKU.WHXB202406014
10. [10]
  Fei Liu , Dong-Yang Zhao , Kai Sun , Ting-Ting Yu , Xin Wang . Comprehensive Experimental Design for Photochemical Synthesis, Analysis, and Characterization of Seleno-Containing Medium-Sized N-Heterocycles. University Chemistry, 2024, 39(3): 369-375. doi: 10.3866/PKU.DXHX202309047
11. [11]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
12. [12]
  Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
13. [13]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
14. [14]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
15. [15]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
16. [16]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
17. [17]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
18. [18]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
19. [19]
  Xiuyun Wang , Jiashuo Cheng , Yiming Wang , Haoyu Wu , Yan Su , Yuzhuo Gao , Xiaoyu Liu , Mingyu Zhao , Chunyan Wang , Miao Cui , Wenfeng Jiang . Improvement of Sodium Ferric Ethylenediaminetetraacetate (NaFeEDTA) Iron Supplement Preparation Experiment. University Chemistry, 2024, 39(2): 340-346. doi: 10.3866/PKU.DXHX202308067
20. [20]
  Jianfeng Yan , Yating Xiao , Xin Zuo , Caixia Lin , Yaofeng Yuan . Comprehensive Chemistry Experimental Design of Ferrocenylphenyl Derivatives. University Chemistry, 2024, 39(4): 329-337. doi: 10.3866/PKU.DXHX202310005

Get Citation

PDF

XML

Metrics

PDF Downloads(36)
Abstract views(1948)
HTML views(341)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142