簡易檢索 / 詳目顯示

研究生: 胡育誠
Yu-Cheng Hu
論文名稱: 陰離子鍵結之氮異環碳烯合成與結構分析及鋯金屬錯合物之研究
Synthesis and Structures of the Amino-Linked N-Heterocyclic Carbenes and C-N Bond Cleavage of its by a Tetrakis(benzyl) Zirconium Complex
指導教授: 陳建添
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2009
畢業學年度: 97
語文別: 英文
論文頁數: 66
中文關鍵詞: 咪唑
英文關鍵詞: Carbene
論文種類: 學術論文
相關次數: 點閱:176下載:0
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • [HC{(R)N(CHCH)N(CH2CH2NHtBu}]Br•HBr, R= MES (1-MES) 或 tBu (1-tBu) 加入過剩的氫氧化鈉得到化合物咪唑鹽類2, [HC{(R)N (CHCH)N(CH2CH2NHtBu}]Br.我們也用了立體障礙較大的2,6-diisopropylaniline去改變側邊臂上胺類基團,得到[2,6-(CH3)2(C6H3)]NHCH2CH2[HC{MESN(CHCH)N}]Br, (2-MES-Anil ian)。
    由NaN(SiMe3)2可將咪唑鹽類2去氫化,而得到咪唑化合物3,由單晶X-Ray繞射分析得知咪唑化合物3-MES透過胺基以及咪唑上的碳(NCN)呈現出分子內彼此相互接觸的結果。
    咪唑化合物3-tBu加入強鹼n-BuLi可得到穩定的金屬鋰咪唑化合物3-tBu.Li,此金屬鋰咪唑化合物為有效穩定高氧化態過渡金屬的轉移試劑,在加入ZrCl4即可得到產率不錯的ZrCl3-NHC, 7. 由X-Ray繞射得知咪唑化合物7為扭曲平面四面體的結構。
    另外,3-MES與3-tBu分別與Zr(Bz)4反應,得到非常特別,具有aza-allyl及η2-N,C咪唑基團的金屬鋯化合物,6-MES和6-tBu。經由中間體5-MES 的結構分析以及動力學的研究,推斷出反應是經由C-H activation導致咪唑側邊臂上碳氮鍵斷裂,而此類型牽涉C-N鍵的斷裂以及在結構上文獻中是前所未有的。

    Treatment of [HC{(R)N(CHCH)N(CH2CH2NHtBu}]Br•HBr, R = MES (1-MES) or tBu (1-tBu) with an excess of NaOH afforded the organic-soluble imidazolium salt 2,[HC{(R)N(CHCH)N(CH2CH2NH tBu}]Br. We also modified an alkyl of amino pendant arm group using bulkier 2,6-diisopropylaniline to afford the [2,6-(CH3)2(C6H3)] NHCH2CH2[HC{MESN(CHCH)N}]Br, (2-MES-Anilian).
    Deprotonation of imidazolium salt 2 by NaN(SiMe3)2 yielded the amino-linked free carbene, 3. The molecular structure of 3-MES was determined by X-ray single-crystal analysis, revealing an unexpectedly close intermolecular contact associated with the carbene and amine through an N-H • • • C interaction.
    Treatment of 3-tBu with n-BuLi gave the more stable Li carbene adduct 3-tBu.Li, which serves as an effective carbene transfer agent to stabilize high oxidation early transition metal and added the ZrCl4 to afford the ZrCl3-NHC, 7 in high yield. X-ray diffraction studies of ZrCl3-NHC confirmed the formation of distorted square planar Zr species, in which the NHC binds via conventional σ-donation of the lone pair to the electrophilic metal center.
    The reaction of Zr(Bz)4 with 3-MES with 3-tBu resulted to a unique meta-stable Zr complex, 6-MES and 6-tBu, possessing an aza-allyl and an η2-N,C-imidazolyl carbene moiety. The crystal structure of 5-MES exhibits an unexpected β-agostic interaction with kinetic investigation believed to involve C-H activation and unprecedented C-N cleavage of the amino-carbene moiety.

    中文摘要……………………………………………………………………………… Abstract…………………………………………………………………………… Chapter 1、Introduction 1.1、What is carbene and type of carbene……………………………1 1.2、What is the NHC carbene and what factors are stabilize for the singlet or triplet…………………………………………2 1.3、NHC carbene in organometallic……………………………………4 1.4、Functional linked NHCs stabilize early transition metal………………………………………………………………………………5 Chapter 2、Result and discussion from NHC Carbene 2.1、Synthesis and Structural Features of the tBu-Amino-Linked MES- Carbene…………………………………………………………7 2.2、Synthesis of Other Bulky Amino-Linked NHCs Carbene Derivatives……………………………………………………………………1 2.3、Summary……………………………………………………………………15 Chapter 3、Result and discussion from Zirconium Complexes of Amino-Linked-NHCs 3.1、Preparation and Characterization of Zr-trichloride Complex Supported by t-Bu-Amino-Linked-t-Bu NHC………………16 3.2、Preparation and Characterization of Zr-tetrabenzyl Complex Supported by t-Bu-Amino-Linked-t-Bu NHC………………19 3.3、Preparation and Characterization of Zr-dibenzyl Complex Supported by t-Bu-Amino-Linked-MES NHC………………22 3.4、Tribenzyl Zr Complex intermediate from 3-MES to 6-MES and Probe the C-N bond Cleavage Mechanism for 5 to 6 Complexes…………………………………………………………………………26 3.5、Experimental observations to favor the pathway A………28 3.6、Summary……………………………………………………………………31 Chapter 4、Experimental Methods and Spectrum data 4.1、General Procedure……………………………………………………32 4.2、Typical procedure for the synthesis of imidazolium salts for tBuNH- CH2CH2[HC{RN(CHCH)N}]Br,(2)……………………33 4.3、Typical procedure for the synthesis of free carbene of tBuNH- CH2CH2[C{RN(CHCH)N}],(3)………………………………………37 4.4、Typical procedure for the synthesis of zirconium complex supported by Amino-Linked NHCs………………………………………………………………………………41 4.5、Kinetic Studies of the Conversion of Complex 5-MES to 6-MES………………………………………………………………………………47 4.6、Reference…………………………………………………………………49 Appendix 1: Single Crystal X-ray Characterization.........................................52 Appendix 2: 1H and 13C spectrum………………………………………66

    1. Hahn, F. E.; Jahnke, M. C. Angew. Chem. lnt. Ed. 2008, 47, 3122-3172.
    2. Guy Bertrand; Didier Bourissou; Olivier Guerret; Francüois P.; Gabba.
    Chem. Rev. 2000, 100, 39-91.
    3. Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290–1309.
    4. N-Heterocyclic Carbenes in Synthesis; Nolan, S. P. Ed.; Wiley-VCH: Weinheim, 2006.
    5. Shin, W.-C.; Wang, C.-H.; Chang, Y.-T.; Glenn, P.-A. Yap.; Ong, T.-G. Organometallics 2009, 28, 1060–1067.
    6. Arnold, P. L.; Liddle, S.T. Chem. Commun. 2006, 3959–3971.
    7. Mungur, S. A.; Blake, A. J.; Claire Wilson; Mcmaster, Jonathan. Arnold, P. L. Organometallics 2006, 25, 1861–1867.
    8. Arnold, P. L.; Mungur, S. A.; Blake, A. J.; Wilson, C. Angew. Chem., Int. Ed. 2003, 42, 5981–5984.
    9. (a) Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361–363. (b) Arduengo, A. J.; Dias, H. V. R.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1992, 114, 5530–5534.
    10. Jong, H.; Patrick, B. O.; Fryzuk, M. D. Can. J. Chem. 2008, 86, 803–810.
    11. (a) Kausamo, A; Tuononen, H. M.; Krahulic, K. E.; Roesler, R. Inorg. Chem. 2008, 47, 1145–1154. (b) Diez-Gonzalez, S.; Nolan, S. P. Coord. Chem. ReV. 2007, 251, 874–883.
    12. Cowan, J. A.; Clyburne, J. A. C.; Davidson, M. G.; Harris, R. L. W.;
    Howard, J. A. K.; Kupper, P.; Leech, M. A.; Richards, S. P. Angew. Chem. Int. Ed. 2002, 41, 1432–1434.
    13. Arnold, P. L.; Mungur, S. A.; Liddle, S. T.; Claire Wilson; Sarsfield Mark J. Chem. Commun. 2004, 23, 2738-2739.
    14. (a) Downing, S. P.; Guadano, S. C.; Pugh, D.; Danopoulos, A. A.; Bellabarba, R. M.; Hanton, M.; Smith, D.; Tooze, R. P. Organometallics 2007, 26, 3762-3770. (b) Niehues, M.; Erker, G.; Kehr, G.; Schwab, P.; Frohlich, R.; Blacque, O.; Berke, H. Organometallics 2002, 21, 2905-2911. (c) Niehues, M.; Erker, G.; Kehr, G.; Wibbeling, B.; Frohlich, R.; Blacque, O.; Berke, H. J. Organomet. Chem. 2002, 192, 663.
    15. Bondi, A. J. Phys. Chem. 1964, 68, 441–451.
    16. (a) Abernethy, C. D.; Codd, G. M.; Spicer, M. D.; Taylor, M. K. J. Am. Chem. Soc. 2003, 125, 1128–1129. (b) Shukla, P.; Johnson, J. A.; Vidovic, D.; Cowley, A. H.; Abernethy, C. D. Chem. Commun. 2004, 360–361.
    17. (a) Scott, M. J.; Lippard, S. J. Inorg. Chim. Acta 1997, 287. (b) Schrock, R. R.; Seidel, S. W.; Schrodi, Y.; Davis, W. M. Organometallics 1999, 18, 428. (c) Zhang, X.; Zhu, Q.; Guzei, I. A.; Jordan, R. F. J. Am. Chem. Soc. 2000, 122, 8093.
    18. (a) Huertos, M. A.; Perez, J.; Riera, L. J. Am. Chem. Soc. 2008, 130, 5662-5663. (b) Huertos, M. A.; Perez, J.; Riera, L.; Menendez- Velazquez, A. J. Am. Chem. Soc. 2008, 130, 13530-13531. (c) Bailey, B. C.; Fan, H.; Huffman, J. C.; Baik, M.-H.; Mindiola, D. J. Am. Chem. Soc. 2006, 128, 6798-6799. (d) Fout, A. R.; Bailey, B. C.; Tomaszewski, J.; Mindiola, D. J. J. Am. Chem. Soc. 2007, 129, 12640-12641. (e) Gray, S. D.;Weller, K. J.; Bruck, M. A.; Briggs, P. M.; Wigley, D. E. J. Am. Chem. Soc. 1995, 117, 10678-10693. (f) Weller, K. J.; Fox, P. A.; Gray, S. D.; Wigley, D. E. Polyhedron 1997, 16, 3139-3163. (g) Klecklry, T. S.; Bennett, J. L.; Wolczabski, P. T.; Lobkovsky, E. B. J. Am. Chem. Soc. 1997, 119, 247-248. (h) Bonanno, J. B.; Veige, A. S.; Wolczanski, P. T.; Lobkovsky, E. B. Inorg. Chim. Acta 2003, 345, 173-184. (i) Neithamer, D. R.; Parkanyi, L.; Mitchell, J. F.; Wolczanski, P. T.; J. Am. Chem. Soc. 1988, 110, 4421-4423. (j) Carver, C. T.; Diaconescu, P. L. J. Am. Chem. Soc. 2008, 130, 7558-7559.
    19. (a) Tsukahara, T.; Swenson, D. C.; Jordan, R. F. Organometallics 1997, 16, 3303-3313. (b) Lee, H.; Jordan, R. F. J. Am. Chem. Soc. 2005, 127, 9384-9385. (c) Girolami, G. S.; Wilkinson,G.; Thornton- Pett, M.; Hursthouse, M. B. J. Chem. Soc. Dalton Trans. 1984, 2789.
    20. (a) Caro, C. F.; Lappert, M. F.; Merle, P. G. Coord. Chem. Rev. 2001, 219, 605-663. (b) Scholz, J.; Kahlert, S.; Gorls, H. Organometallics 2004, 23, 1594-1603. (c) Lappert, M. F.; Liu, D.-Sh. J. Organomet. Chem. 1995, 500, 203-217. (d) Hitchcock, P. B.; Lappert, M. F.; Liu, D-Sh.; Ryan, E. J. Polyhedron 1995, 14, 2745-2752.
    21. Allen, F. H.; Kennard, O.; Waston, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R.J. Chem. Soc., Perkin Trans. 2 1978, S1-S19.
    22. (a) Rottger, D.; Erker, G.; Frohlich, R.; Kotila, S. J. Organomet. Chem 1996, 17-19. (b) Ishiyama, T.; Mizuta, T.; Miyoshi, K.; Nakazawa, H. Organometallics 2003, 22, 1096-1105.
    23. (a) Sundberg, R. J.; Bryan, R. F.; Taylor, I. F., Jr.; Taube, H. J. Am. Chem. Soc. 1974, 96, 381. (b) Burling, S.; Mahon, M. F. Powell, R. E.; Whittlesey, M. K.; Williams, J. M. J. J. Am. Chem. Soc. 2006, 128, 13702-13703.

    無法下載圖示 本全文未授權公開
    QR CODE