Citation: Cui Haiyan, Cui Chunming. Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes[J]. Chinese Journal of Organic Chemistry, ;2016, 36(3): 626-629. doi: 10.6023/cjoc201511002 shu

Base-Stabilized 1-Hydrosilaimine: Reactivity of Diaminochlorosilane toward N-Heterocyclic Carbenes

Cui Haiyan ^a,, ,
Cui Chunming ^b,,

1.
a Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing 210095;
2.
b State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071

Corresponding author: Cui Haiyan, Cui Chunming,
Received Date: 2 November 2015
Available Online: 21 November 2015
Fund Project: 中央高校基本科研业务费(No. KJQN201551) (No. KJQN201551)国家自然科学基金(No. 21402094) (No. 21402094)江苏省科技计划项目(No. BK20140678) (No. BK20140678)国家重点基础研究发展规划(973计划, No. 2012CB821600)资助项目. (973计划, No. 2012CB821600)

Studies on the formation of silaimines are among the most fascinating topics in organosilicon chemistry. The first route to silaimine via eliminaition of Me₃SiCl from diaminochlorosilanes is reported. Reaction of aminodichlorosilane ArN(SiMe₃)SiHCl₂ (1) (Ar=2,6-i-Pr₂C₆H₃) with ArN(SiMe₃)Li in Et₂O at -78 ℃ followed by stirring the mixture for 5 h at room temperature afforded diaminochlorosilane [ArN(SiMe₃)]₂SiHCl (2). Compound 2 has been fully characterized by ¹H NMR, ¹³C NMR, ²⁹Si NMR, IR and elemental analysis. Reactivity of 2 with different N-heterocyclic carbenes has been examined. It was found that 2 did not react with sterically hindered N-heterocyclic carbenes (NHC), 3-tert-butylimidazol-2-ylidene (ItBu) and 1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene (IiPr) at room temperature or under reflux conditions. However, compound 2 could react with one equivalent of 1,3,4,5-tetramethyl-imidazol-2-ylidene (IMe₄) to give base-stabilized 1-hydrosilaimine 3. Compound 3 can be viewed as the elimination product from 2 through loss of Me₃SiCl, as the small IMe₄ coordinate to 2 to form a hypervalent silicon species.
- chlorosilanes,
- N-heterocyclic carbenes,
- silaimines
1. [1]
  [1](a) Xiong, Y.; Yao, S.; Driess, M. Angew. Chem., Int. Ed. 2013, 52, 4302.
2. [2]
  (b) Fischer, R. C.; Power, P. P. Chem. Rev. 2010, 110, 3877.
3. [3]
  (c) Power, P. P. Chem. Rev. 1999, 99, 3463.
4. [4]
  [2](a) Muck, F. M.; Ulmer, A.; Baus, J. A.; Burschka, C.; Tacke, R. Eur. J. Inorg. Chem. 2015, 1860.
5. [5]
  (b) Cui, H.; Ma, B.; Cui, C. Organometallics 2012, 31, 7339.
6. [6]
  (c) Kocher, N.; Henn, J.; Gostevskii, B.; Kost, D.; Kalikhman, I.; Engels, B.; Stalke, D. J. Am. Chem. Soc. 2004, 126, 5563.
7. [7]
  (d) Kocher, N.; Selinka, C.; Leusser, D.; Kost, D.; Kalikhman, I.; Stalke, D. Z. Anorg. Allg. Chem. 2004, 630, 1777.
8. [8]
  (e) Niessmann, J.; Klingebiel, U.; Schäfer, M.; Boese, R. Organometallics 1998, 17, 947.
9. [9]
  (f) Denk, M.; Hayashi, R.; West, R. J. Am. Chem. Soc. 1994, 116, 10813.
10. [10]
  (g) Stalke, D.; Klingebiel, U.; Sheldrick, G. M. J. Organomet. Chem. 1988, 344, 37.
11. [11]
  [3](a) Wiberg, N.; Schurz, K.; Fischer, G. Angew. Chem., Int. Ed. Engl. 1985, 24, 1053.
12. [12]
  (b) Wiberg, N.; Schurz, K.; Reber, G.; Müller, G. J. Chem. Soc., Chem., Commun. 1986, 591.
13. [13]
  (c) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649.
14. [14]
  [4](a) Azhakar, R.; Roesky, H. W.; Holstein, J. J.; Pröpper, K.; Dittrich, B. Organometallics 2013, 32, 358.
15. [15]
  (b) Samuel, P. P.; Azhakar, R.; Ghadwal, R. S.; Sen, S. S.; Roesky, H. W.; Granitzka, M.; Matussek, J.; Herbst-Irmer, R.; Stalke, D. Inorg. Chem. 2012, 51, 11049.
16. [16]
  (c) Zhang, S.-H.; Yeong, H.-X.; So, C.-W. Chem.-Eur. J. 2011, 17, 3490.
17. [17]
  (d) Kong, L.; Cui, C. Organometallics 2010, 29, 5738.
18. [18]
  (e) Iwamoto, T.; Ohnishi, N.; Gui, Z.; Ishida, S.; Isobe, H.; Maeda, S.; Ohno, K.; Kira, M. New J. Chem. 2010, 34, 1637.
19. [19]
  [5](a) Khan, S.; Sen, S. S.; Kratzert, D.; Tavčar, G.; Roesky, H. W.; Stalke, D. Chem.-Eur. J. 2011, 17, 4283.
20. [20]
  (b) Ghadwal, R. S.; Roesky, H. W.; Schulzke, C.; Granitzka, M. Organometallics 2010, 29, 6329.
21. [21]
  [6] Cui, H.; Cui, C. Chem.-Asian J. 2011, 6, 1138.
22. [22]
  [7](a) Hssf, M.; Schmedake, T. A.; West, R. Acc. Chem. Res. 2000, 33, 704.
23. [23]
  (b) Driess, M.; Block, S.; Brym, M.; Gamer, M. T. Angew. Chem., Int. Ed. 2006, 45, 2293.
24. [24]
  [8] Denk, M.; Lennon, R.; Hayashi, R.; West, R.; Belyakov, A. V.; Verne, H. P.; Haaland, A.; Wagner, M.; Metzler, N. J. Am. Chem. Soc. 1994, 116, 2691.
25. [25]
  [9](a) Inoue, S.; Leszczyńska, K., Angew. Chem., Int. Ed. 2012, 51, 8589.
26. [26]
  (b) Asay, M.; Inoue, S.; Driess, M., Angew. Chem., Int. Ed. 2011, 50, 9589.
27. [27]
  (c) Jutzi, P.; Leszczyńska, K.; Neumann, B.; Schoeller, W. W.; Stammler, H.-G. Angew. Chem., Int. Ed. 2009, 48, 2596.
28. [28]
  (d) Driess, M.; Yao, S.; Brym, M.; van Wüllen, C.; Lentz, D. J. Am. Chem. Soc. 2006, 128, 9628.
29. [29]
  (e) So, C.-W.; Roesky, H. W.; Magull, J.; Oswald, R. B. Angew. Chem., Int. Ed. 2006, 45, 3948.
30. [30]
  (f) Kira, M.; Ishida, S.; Iwamoto, T.; Kabuto, C. J. Am. Chem. Soc. 1999, 121, 9722.
31. [31]
  (g) Gehrhus, B.; Lappert, M. F.; Heinicke, J.; Boese, R.; Bläser, D. J. Chem. Soc., Chem. Commun. 1995, 1931.
32. [32]
  [10] Cui, H.; Shao, Y.; Li, X.; Kong, L.; Cui, C. Organometallics 2009, 28, 5191.
33. [33]
  [11] Ghadwal, R. S.; Roesky, H. W.; Merkel, S.; Henn, J.; Stalke, D. Angew. Chem., Int. Ed. 2009, 48, 5683.
34. [34]
  [12](a) Agou, T.; Hayakawa, N.; Sasamori, T.; Matsuo, T.; Hashizume, D.; Tokitoh, N. Chem.-Eur. J. 2014, 20, 9246.
35. [35]
  (b) Inoue, S.; Eisenhut, C. J. Am. Chem. Soc. 2013, 135, 18315.
36. [36]
  (c) Al-Rafia, S. M. I.; McDonald, R.; Ferguson, M. J.; Rivard, E. Chem.-Eur. J. 2012, 18, 13810.
37. [37]
  (d) Tanaka, H.; Ichinohe, M.; Sekiguchi, A. J. Am. Chem. Soc. 2012, 134, 5540.
38. [38]
  (e) Ghadwal, R. S.; Roesky, H. W.; Merkel, S.; Henn, J.; Stalke, D. Angew. Chem., Int. Ed. 2009, 48, 5683.
39. [39]
  (f) Filippou, A. C.; Chernov, O.; Schnakenburg, G. Angew. Chem., Int. Ed. 2009, 48, 5687.
40. [40]
  [13](a) Filippou, A. C.; Chernov, O.; Blom, B.; Stumpf, K. W.; Schnakenburg, G. Chem.-Eur. J. 2010, 16, 2866.
41. [41]
  (b) Gao, Y.; Zhang, J.; Hu, H.; Cui, C. Organometallics 2010, 29, 3063.
42. [42]
  [14] Cui, H.; Cui, C. Dalton Trans. 2011, 40, 11937.
43. [43]
  [15] Scott, N. M.; Dorta, R.; Stevens, E. D.; Correa, A.; Cavallo, L.; Nolan, S. P. J. Am. Chem. Soc. 2005, 127, 3516.
44. [44]
  [16] Kuhn, N.; Kratz, T. Synthesis 1993, 561.
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