Citation: Wang Peng, Xiao Jie, Leng Xuebing, Deng Liang. A High-Spin Iron(II) Complex Supported by a Tridentate Diamido-stibine Ligand: Synthesis, Structure and Its Reactions with Organic Azides and Diazo Compounds[J]. Chinese Journal of Organic Chemistry, ;2019, 39(8): 2243-2250. doi: 10.6023/cjoc201904040 shu

A High-Spin Iron(II) Complex Supported by a Tridentate Diamido-stibine Ligand: Synthesis, Structure and Its Reactions with Organic Azides and Diazo Compounds

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Deng Liang, deng@sioc.ac.cn
Received Date: 16 April 2019
Revised Date: 13 May 2019
Available Online: 21 August 2019
Fund Project: the Strategic Priority Research Program of Chinese Academy of Sciences XDB20000000the National Key Research and Development Program of the Ministry of Science and Technology 2016YFA0202900the National Natural Science Foundation of China 21690062the National Natural Science Foundation of China 21725104Project supported by the National Key Research and Development Program of the Ministry of Science and Technology (No. 2016YFA0202900), the National Natural Science Foundation of China (Nos. 21725104, 21690062, 21432001, 21821002), the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB20000000), and the Program of Shanghai Academic Research Leader (No. 19XD1424800)the Program of Shanghai Academic Research Leader 19XD1424800the National Natural Science Foundation of China 21432001the National Natural Science Foundation of China 21821002

Figures(10)

Treatment of PhSbCl₂ with 2 equiv. of (2, 6-Cl₂C₆H₃)(2-LiC₆H₄)NLi, which was generated in situ by the interaction of (2, 6-Cl₂C₆H₃)(2-BrC₆H₄)NH with 2 equiv. of BuⁿLi, followed by quenching with water, afforded the diamine-stibine compound ((o-(N-(2, 6-Cl₂C₆H₃)NH)C₆H₄)₂SbPh (denoted as H₂(^dcpN₂Sb)). H₂(^dcpN₂Sb) undergoes amine-elimination reaction with[Fe(N(SiMe₃)₂)₂]₂ (0.5 euiqv.) to afford an iron(Ⅱ) complex[(κ³-N, N, Sb-^dcpN₂Sb)Fe(THF)] (1) bearing an unique tridentate bisamido-stibine ligand. Solution magnetic susceptibility measurements (μ_eff=4.7(2) μ_B in C₆D₆) reveal a high spin (S=2) electronic structure for 1. Complex 1 represents the first high-spin iron(Ⅱ) complex with organic stibine ligation, and features a long Fe-Sb bond distance of 0.2792(1) nm. Density functional theory (DFT) calculations indicate weak σ interaction betwen the high-spin iron(Ⅱ) center and the antimony atom due to ineffective orbital overlap. Complex 1 can react with organic azides RN₃ to furnish the high-spin (S=2) iron(Ⅱ) complexes that bear tridentate bisamido-stibonium imine ligands[(κ³-N, N, N-^dcpN₂SbN^R)Fe(py)] (R=dcp (2, 6-Cl₂C₆H₃), 2; R=Dipp (2, 6-ⁱPr₂C₆H₃), 3). These compexes are among the rare metal complexes with stibonium imine ligation. The average Sb-N distance of 0.194 nm in the imine moieties is found comparable to those of the Sb-N bonds in the reported stibonium imine compounds Mes₃SbNCOCl₃ (0.199 nm) and 2-MeC₆H₄)₃SbNSO₂CF₃ (0.196 nm). The reactions of 1 with diazo compounds (R¹R²)CN₂ afford the high-spin iron(Ⅱ) complexes featuring tridentate bisamido-stibonium ylide ligands[(κ³-N, N, C-^dcpN₂SbC^{R1, R2})Fe(PMe₃)] (R¹=H, R²=CO₂Bu^t, 4; R¹=Ph, R²=CO₂Et, 5). The average Sb-C distance of 0.206 nm in the ylide moieties is found comparable to those of the Sb-C bonds in the reported stibonium ylide compounds (around 0.20 nm). H₂(^dcpN₂Sb) and 1~5 have been characterized by elemental analysis, ¹H NMR, solution magnetic susceptibility measurements and single-crystal X-ray diffraction studies.
- antimony,
- iron,
- imine,
- ylide,
- high-spin
1. [1]
  Levason, W.; Mcauliffe, C. A. Acc. Chem. Res. 1978, 11, 363. doi: 10.1021/ar50129a007
2. [2]
  Champness, N. R.; Levason, W. Coord. Chem. Rev. 1994, 133, 115. doi: 10.1016/0010-8545(94)80058-8
3. [3]
  Levason, W.; Reid, G. Coord. Chem. Rev. 2006, 250, 2565. doi: 10.1016/j.ccr.2006.03.024
4. [4]
  Jones, J. S.; Gabbai, F. P. Acc. Chem. Res. 2016, 49, 857. doi: 10.1021/acs.accounts.5b00543
5. [5]
  Breunig, H. J.; Borrmann, T.; Lork, E.; Moldovan, O.; Raţ, C. I.; Wagner, R. P. J. Organomet. Chem. 2009, 694, 427. doi: 10.1016/j.jorganchem.2008.11.022
6. [6]
  Genge, A. R. J.; Holmes, N. J.; Levason, W.; Webster, M. Polyhedron 1999, 18, 2673. doi: 10.1016/S0277-5387(99)00168-0
7. [7]
  Bryan, R. F.; Schmidt, W. C. J. Chem. Soc., Dalton Trans. 1974, 2337.
8. [8]
  Benjamin, S. L.; Karagiannidis, L.; Levason, W.; Reid, G.; Rogers, M. C. Organometallics 2011, 30, 895. doi: 10.1021/om1010148
9. [9]
  Godfrey, S. M.; McAuliffe, C. A.; Pritchard, R. G. J. Chem. Soc., Chem. Commun. 1994, 45.
10. [10]
  Jones, J. S.; Wade, C. R.; Gabbai, F. P. Angew. Chem., Int. Ed. 2014, 53, 8876. doi: 10.1002/anie.201404156
11. [11]
  Mo, Z.; Deng, L. Coord. Chem. Rev. 2017, 350, 285. doi: 10.1016/j.ccr.2017.07.007
12. [12]
  Poli, R. Chem. Rev. 1996, 96, 2135. doi: 10.1021/cr9500343
13. [13]
  Power, P. P. Chem. Rev. 2012, 112, 3482. doi: 10.1021/cr2004647
14. [14]
  Xiao, J.; Deng, L. Dalton Trans. 2013, 42, 5607. doi: 10.1039/c3dt50518a
15. [15]
  Zhao, M.; Mao, G.; Liu, Y.; Xiao, J.; Deng, L. Chin. J. Org. Chem. 2018, 38, 1656. doi: 10.6023/cjoc201803015
16. [16]
  Bojan, V. R.; Fernandez, E. J.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge, M.; Olmos, M. E.; Puelles, R. C.; Silvestru, C. Inorg. Chem. 2010, 49, 5530. doi: 10.1021/ic1003484
17. [17]
  Slater, J. C. J. Chem. Phys. 1964, 41, 3199. doi: 10.1063/1.1725697
18. [18]
  Alvarez, S. Dalton Trans. 2013, 42, 8617. doi: 10.1039/c3dt50599e
19. [19]
  Liu, J.; Hu, L.; Wang, L.; Chen, H.; Deng, L. J. Am. Chem. Soc. 2017, 139, 3876. doi: 10.1021/jacs.7b00484
20. [20]
  You, D.; Yang, H. F.; Sen, S.; Gabba , F. P. J. Am. Chem. Soc. 2018, 140, 9644. doi: 10.1021/jacs.8b05520
21. [21]
  Wade, C. R.; Gabbai, F. P. Angew. Chem., Int. Ed. 2011, 50, 7369. doi: 10.1002/anie.201103109
22. [22]
  Matano, Y.; Nomura, H.; Suzuki, H.; Shiro, M.; Nakano, H. J. Am. Chem. Soc. 2001, 123, 10954. doi: 10.1021/ja003623l
23. [23]
  Matano, Y.; Nomura, H.; Suzuki, H. Inorg. Chem. 2000, 39, 1340. doi: 10.1021/ic991120e
24. [24]
  Edwards, A. J.; Paver, M. A.; Raithby, P. R.; Russell, C. A.; Wright, D. S. J. Chem. Soc., Dalton Trans. 1993, 2257.
25. [25]
  Edwards, A. J.; Paver, M. A.; Rennie, M.-A.; Raithby, P. R.; Russell, C. A.; Wright, D. S. J. Chem. Soc., Dalton Trans. 1994, 2963.
26. [26]
  Burford, N.; Macdonald, C. L. B.; Robertson, K. N.; Cameron, T. S. Inorg. Chem. 1996, 35, 4013. doi: 10.1021/ic951532x
27. [27]
  Burford, N.; Cameron, T. S.; Lam, K. C.; LeBlanc, D. J.; Macdonald, C. L. B.; Phillips, A. D.; Rheingold, A. L.; Stark, L.; Walsh, D. Can. J. Chem. 2001, 79, 342. doi: 10.1139/v01-057
28. [28]
  Glidewell, C.; Lloyd, D.; Metcalfe, S. Tetrahedron 1986, 42, 3887. doi: 10.1016/S0040-4020(01)87542-6
29. [29]
  Ferguson, G.; Glidewell, C.; Gosney, I.; Lloyd, D.; Metcalfe, S.; Lumbroso, H. J. Chem. Soc., Perkin Trans. 2 1988, 1829.
30. [30]
  Koketsu, J.; Ninomiya, Y.; Suzuki, Y.; Koga, N. Inorg. Chem. 1997, 36, 694. doi: 10.1021/ic951220u
31. [31]
  Sudhakar, P. V.; Lammertsma, K. J. Am. Chem. Soc. 1991, 113, 1899. doi: 10.1021/ja00006a005
32. [32]
  Evans, D. F. J. Chem. Soc. 1959, 2003.
33. [33]
  Sur, S. K. J. Magn. Reson. 1989, 82, 169.
34. [34]
  Chalmers, B. A.; Buhl, M.; Arachchige, K. S. A.; Slawin, A. M. Z.; Kilian, P. Chem. Eur. J. 2015, 21, 7520. doi: 10.1002/chem.201500281
35. [35]
  Olmstead, M. M.; Power, P. P.; Shoner, S. C. Inorg. Chem. 1991, 30, 2547. doi: 10.1021/ic00011a017
36. [36]
  Neese, F. ORCA-an ab initio, Density Functional and Semi-empirical Program Package (v.3.0.3), Max-Planck Institute for Bioinorganic Chemistry, Mülheim an der Ruhr, Germany, 2015.
37. [37]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
38. [38]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B:Condens. Matter Mater. Phys. 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
39. [39]
  Schafer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829. doi: 10.1063/1.467146
40. [40]
  Schafer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571. doi: 10.1063/1.463096
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