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研究生:詹立暐
研究生(外文):Li-Wei Chan
論文名稱:三芽氮異環碳烯之重元素相似物的合成與鑑定
論文名稱(外文):Syntheses of Tritopic N-Heterocyclic Metallylenes
指導教授:邱靜雯
口試委員:詹益慈王志傑
口試日期:2013-06-28
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:英文
論文頁數:104
中文關鍵詞:矽烯鍺烯錫烯鉛烯均三甲苯叔丁基三亞苯
外文關鍵詞:metallylenesilylenegermylenestannyleneplumbylene
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單芽氮異環碳烯之重元素相似物的性質及配位特性已經被研究了數十年,並
且在這方面有顯著的成果。然而,在單一分子中具有兩個以上的氮異環碳烯重元
素相似物卻是非常少見。因此,在本篇論文中,我們以合成具有高對稱性的多牙
氮異環碳烯重元素相似物為目標,其中包含了鍺烯、錫烯、r 及鉛烯,並對其做鑑
定及反應性的探討。在分子設計的部分,我們藉由立障極大的取代基,如:均三
甲苯和叔丁基,來穩定碳烯重元素相似物中的空軌域,並且以三亞苯作為分子骨
架來達成高對稱性分子的目的。鍺烯、錫烯、及鉛烯的合成,可以利用二價的鍺、
錫、鉛的前驅物,利用取代反應來獲得,並且以異核核磁共振光譜來證明其存在。
在矽烯的合成方面,我們先和成了四價的矽烷前驅物,之後再以強還原試劑將四
價矽還原成二價矽,但是在經過許多嘗試後,還是無法達到預期的結果。

Being the heavier analogues of N-heterocyclic carbene, the coordination chemistry
of the so-called NHE (E = Si, Ge, Sn, Pb) have been investigated for decades. However,
while significant progresses were made in poly-NHCs, molecules bearing multiple NHE
units have only been reported few times. In this work, the syntheses of symmetrically
N,N’-substituted tritopic metallylenes featuring a rigid molecular backbone will be
presented. Tritopic NHSi precursors, dichlorosilanes, obtained from deprotonated
hexa-(alkylamino)triphenylene and SiCl4 failed in generating tri-silylene from chemical
reductions with K, KC8, and LiNp. On the other hand, reaction of deprotonated
hexamine and ECl2 (E = Sn, Pb) gives the desired tritopic metallylenes, which can also
be prepared from the reaction of hexamine and E[N(TMS)2]2 (E = Ge, Sn, Pb). The only
exception is the reaction of hexa-(tert-butylamino)triphenylene and Sn[N(TMS)2]2 that
yields the imine coordinated stannylene.

口試委員會審定書 ............................................................................................................i
中文摘要 .......................................................................................................................... ii
ABSTRACT .................................................................................................................... iii
CONTENTS .....................................................................................................................iv
LIST OF FIGURES ..........................................................................................................vi
LIST OF SCHEMES ..................................................................................................... viii
Chapter 1 Introduction .............................................................................................. 1
1.1 Carbene ........................................................................................................... 1
1.2 Metallylenes .................................................................................................... 4
1.2.1 Silylene .................................................................................................. 4
1.2.2 Germylene ............................................................................................. 6
1.2.3 Stannylene ............................................................................................. 9
1.2.4 Plumbylene .......................................................................................... 11
1.3 Reactivity of Metallylenes ............................................................................ 13
1.4 Research Objective ....................................................................................... 15
Chapter 2 Molecular Design and Synthetic Methods ........................................... 18
2.1 Molecular Design.......................................................................................... 18
2.2 Synthetic Methods ........................................................................................ 20
Chapter 3 Results and Discussion ........................................................................... 23
3.1 Synthesis of Hexaminotriphenylenes ........................................................... 23
3.2 Synthesis of N-Heterocyclic Silylenes.......................................................... 24
3.3 Synthesis of N-Heterocyclic Germylenes ..................................................... 26
3.4 Synthesis of N-Heterocyclic Stannylenes ..................................................... 28
v
3.5 Synthesis of N-Heterocyclic Plumbylenes.................................................... 32
3.6 UV-Vis Spectrum of N-Heterocyclic Metallylenes ...................................... 35
3.7 Reactivities of N-Heterocyclic Metallylenes ................................................ 36
Chapter 4 Conclusions ............................................................................................. 38
Chapter 5 Experimental Section ............................................................................. 39
REFERENCES ................................................................................................................ 50
APPENDIX…………………………………………………………………………….54

1. Fevre, M.; Pinaud, J.; Gnanou, Y.; Vignolle, J.; Taton, D., Chem. Soc. Rev. 2013, 42,
2142-2172.
2. Velazquez, H. D.; Verpoort, F., Chem. Soc. Rev. 2012, 41, 7032-7060.
3. Liu, W.; Gust, R., Chem. Soc. Rev. 2013, 42, 755-773.
4. (a) Holthausen, M. C.; Koch, W.; Apeloig, Y., J. Am. Chem. Soc. 1999, 121,
2623-2624; (b) Sekiguchi, A.; Tanaka, T.; Ichinohe, M.; Akiyama, K.; Tero-Kubota,
S., J. Am. Chem. Soc. 2003, 125, 4962-4963.
5. Arduengo, A. J.; Harlow, R. L.; Kline, M., J. Am. Chem. Soc. 1991, 113, 361-363.
6. 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, 2691-2692.
7. Kong, L.; Zhang, J.; Song, H.; Cui, C., Dalton Trans. 2009, 0, 5444-5446.
8. Schmedake, T. A.; Haaf, M.; Apeloig, Y.; Muller, T.; Bukalov, S.; West, R., J. Am.
Chem. Soc. 1999, 121, 9479-9480.
9. (a) Li, W.; Hill, N. J.; Tomasik, A. C.; Bikzhanova, G.; West, R., Organometallics
2006, 25, 3802-3805; (b) Tomasik, A. C.; Mitra, A.; West, R., Organometallics
2008, 28, 378-381.
10. (a) Gehrhus, B.; Lappert, M. F.; Heinicke, J.; Boese, R.; Blaser, D., J. Chem. Soc.,
Chem. Commun. 1995, 0, 1931-1932; (b) Heinicke, J.; Oprea, A.; Kindermann, M.
K.; Karpati, T.; Nyulaszi, L.; Veszpremi, T., Chem. Eur. J. 1998, 4, 541-545.
11. Kira, M.; Ishida, S.; Iwamoto, T.; Kabuto, C., J. Am. Chem. Soc. 1999, 121,
9722-9723.
12. Lee, G.-H.; West, R.; Muller, T., J. Am. Chem. Soc. 2003, 125, 8114-8115.
13. Jutzi, P.; Kanne, D.; Kruger, C., Angew. Chem., Int. Ed. Engl. 1986, 25, 164-164.
51
14. (a) Rekken, B. D.; Brown, T. M.; Fettinger, J. C.; Tuononen, H. M.; Power, P. P., J.
Am. Chem. Soc. 2012, 134, 6504-6507; (b) Protchenko, A. V.; Birjkumar, K. H.;
Dange, D.; Schwarz, A. D.; Vidovic, D.; Jones, C.; Kaltsoyannis, N.; Mountford, P.;
Aldridge, S., J. Am. Chem. Soc. 2012, 134, 6500-6503.
15. Davidson, P. J.; Harris, D. H.; Lappert, M. F., J. Chem. Soc., Dalton Trans. 1976, 0,
2268-2274.
16. Jutzi, P.; Becker, A.; Stammler, H. G.; Neumann, B., Organometallics 1991, 10,
1647-1648.
17. Mitsuo Kira, S. I., Takeaki Iwamoto, Masaaki Ichinohe, Chizuko Kabuto, Lubov
Ignatovich, and Hideki Sakurai, Chem. Lett. 1999, 263.
18. Jutzi, P.; Schmidt, H.; Neumann, B.; Stammler, H.-G., Organometallics 1996, 15,
741-746.
19. M. Veith, M. G., Z., Zeitschrift fur Naturforschung 1982, 37b, 1375-1381.
20. Pfeiffer, J.; Maringgele, W.; Noltemeyer, M.; Meller, A., Chem. Ber. 1989, 122,
245-252.
21. Herrmann, W. A.; Denk, M.; Behm, J.; Scherer, W.; Klingan, F.-R.; Bock, H.;
Solouki, B.; Wagner, M., Angew. Chem., Int. Ed. Engl. 1992, 31, 1485-1488.
22. Meller, A.; Grabe, C.-P., Chem. Ber. 1985, 118, 2020-2029.
23. Zabula, A. V.; Hahn, F. E.; Pape, T.; Hepp, A., Organometallics 2007, 26,
1972-1980.
24. Fischer, E. O. G., H., Z. Naturforsch. 1956, B11, 423.
25. Kira, M.; Yauchibara, R.; Hirano, R.; Kabuto, C.; Sakurai, H., J. Am. Chem. Soc.
1991, 113, 7785-7787.
26. Harris, D. H.; Lappert, M. F., J. Chem. Soc., Chem. Commun. 1974, 0, 895-896.
27. Veith, M., Z. Naturforsch. 1978, 33b, 1.
28. (a) Braunschweig, H.; Gehrhus, B.; Hitchcock, P. B.; Lappert, M. F., Z. Anorg. Allg.
Chem. 1995, 621, 1922-1928; (b) Dias, H. V. R.; Jin, W., J. Am. Chem. Soc. 1996,
118, 9123-9126; (c) Drost, C.; Hitchcock, P. B.; Lappert, M. F., Angew. Chem. Int.
Ed. 1999, 38, 1113-1116.
29. Hahn, F. E.; Wittenbecher, L.; Le Van, D.; Zabula, A. V., Inorg. Chem. 2007, 46,
7662-7667.
30. Fischer, E. O.; Grubert, H., Z. Anorg. Allg. Chem. 1956, 286, 237-242.
31. Simons, R. S.; Pu, L.; Olmstead, M. M.; Power, P. P., Organometallics 1997, 16,
1920-1925.
32. Kano, N.; Shibata, K.; Tokitoh, N.; Okazaki, R., Organometallics 1999, 18,
2999-3007.
33. Charmant, J. P. H.; Haddow, M. F.; Hahn, F. E.; Heitmann, D.; Frohlich, R.;
Mansell, S. M.; Russell, C. A.; Wass, D. F., Dalton Trans. 2008, 0, 6055-6059.
34. Hahn, F. E.; Heitmann, D.; Pape, T., Eur. J. Inorg. Chem. 2008, 2008, 1039-1041.
35. Heitmann, D.; Pape, T.; Hepp, A.; Muck-Lichtenfeld, C.; Grimme, S.; Hahn, F. E., J.
Am. Chem. Soc. 2011, 133, 11118-11120.
36. Matsumoto, T.; Tokitoh, N.; Okazaki, R., J. Am. Chem. Soc. 1999, 121, 8811-8824.
37. Boydston, A. J.; Bielawski, C. W., Dalton Trans. 2006, 0, 4073-4077.
38. Boydston, A. J.; Williams, K. A.; Bielawski, C. W., J. Am. Chem. Soc. 2005, 127,
12496-12497.
39. Krupski, S.; Dickschat, J. V.; Hepp, A.; Pape, T.; Hahn, F. E., Organometallics 2012,
31, 2078-2084.
40. Oka, K.; Nakao, R., Res. Chem. Intermed. 1990, 13, 143-148.
41. Tokitoh, N.; Matsumoto, T.; Manmaru, K.; Okazaki, R., J. Am. Chem. Soc. 1993,
115, 8855-8856.
42. (a) Eaborn, C.; Ganicz, T.; Hitchcock, P. B.; Smith, J. D.; Sozerli, S. E.,
Organometallics 1997, 16, 5621-5622; (b) Eaborn, C.; Hill, M. S.; Hitchcock, P. B.;
Patel, D.; Smith, J. D.; Zhang, S., Organometallics 1999, 19, 49-53.
43. Denk, R. W. a. M., Pure Appl. Chem. 1996, 68, 785-788.
44. Arp, H.; Baumgartner, J.; Marschner, C.; Muller, T., J. Am. Chem. Soc. 2011, 133,
5632-5635.
45. Dybowski, C.; Altounian, N.; Glatfelter, A.; Bai, S., J. Phys. Chem. B 2000, 104,
4723-4725.
46. Weitz, I. S.; Rabinovitz, M., J. Chem. Soc., Perkin Trans. 1 1993, 0, 117-120.
47. Suzuki, H.; Tokitoh, N.; Okazaki, R.; Harada, J.; Ogawa, K.; Tomoda, S.; Goto, M.,
Organometallics 1995, 14, 1016-1022.
48. Jafarpour, L.; Stevens, E. D.; Nolan, S. P., J. Organomet. Chem. 2000, 606, 49-54.
49. Lemierre, V.; Chrostowska, A.; Dargelos, A.; Baylere, P.; Leigh, W. J.; Harrington,
C. R., Appl. Organomet. Chem. 2004, 18, 676-683.
50. Yatabe, T.; Harbison, M. A.; Brand, J. D.; Wagner, M.; Mullen, K.; Samori, P.; Rabe,
J. P., J. Mater. Chem. 2000, 10, 1519-1525.

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