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研究生:蕭竣
研究生(外文):Jun Hsiao
論文名稱:應用密度泛函數理論計算於金屬錯合物催化反應:I. 以二茂鐵或含鈷之類三明治雙牙磷基配位之衍生鈀金屬錯合物催化Suzuki-Miyaura偶合反應II. 以含氮雜環碳烯-
論文名稱(外文):DFT Studies on Metal-containing Complexes Catalyzed Reactions:I. Suzuki-Miyaura Reactions Catalyzed by Ferrocenyl or Cobaltocenyl Phosphines Ligated Palladium ComplexesII. Allylic Aminations Catalyzed by N-Heterocyclic Carbene-Pyridine Ligated Palladium
指導教授:洪豐裕
指導教授(外文):Fung-E Hong
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學系所
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:2010
畢業學年度:98
語文別:中文
論文頁數:88
中文關鍵詞:密度泛函數理論理論記算二茂鐵催化反應碳烯鈀金屬丙烯基胺化反應
外文關鍵詞:Density functional theoryDFTFerroceneSuzuki-MiyauraCoupling reactionN-heterocyclic carbenePalladiumallylic amination
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在Part I的研究中,密度泛函數理論方法被使用於計算多種二茂鐵及含鈷之類三明治雙牙膦基配位之衍生鈀金屬錯合物應用於Suzuki耦合催化反應。結果非預期地得到在同一環上之膦配位基比在不同環上之膦配位基較具優勢的結論。在所有計算實例中,若使用1,2-dmpf或1,2-dmpc之配位基,反應途徑能量趨勢而言是最佳的。此外,二級氧化膦基對本篇研究之耦合反應較不具優勢,除非目的為應用於保存使用。

In topic part I, several dppf- and dppc-derived bidentate phosphines ligated palladium complexes catalyzed Suzuki-Miyaura reactions have been studied using density functional theory. Unexpectedly, the catalytic reactions employing ligands having two phosphine biting sites on the same cyclpentadienyl or cyclobutadiene ring, such as 1,2-dmpf or 1,2-dmpc, had been verified energetically more favorable than those on different rings. The application of a secondary phosphine oxide in coupling reaction is an unfavorable choice unless for the purpose of storage.

Topic Part II
Allylic Aminations Catalyzed by N-Heterocyclic Carbene-Pyridine Ligated Palladium Complexes

Abstract
The allylic aminations catalyzed by N-heterocyclic carbene-pyridine ligated palladium complexes have been studied by using density functional theory (B3LYP/LanL2DZ). All the geometries were fully optimized, and the potential energy surfaces for the allylic aminations have been discussed in detail. Comparison of the activation barriers and reaction enthalpies were used to determine the relative reactivities of the potential diastereomers of cationic palladium-allyl complexes. As a result, the theoretical investigation suggests that the nucleophilic addition on the syn-allyl fragment is a more favorable pathway for the allylic aminations. These calculations are consistent with the experimental results.


目錄
一、序論…………………………………………………………… 1
第一節 密度泛函數理論簡介…………………………………… 2
第二節 基底函數………………………………………………… 6
第三節 計算方法………………………………………………… 10
二、參考文獻……………………………………………………… 14

Topic Part I 以二茂鐵或含鈷之類三明治雙牙磷基配位之衍生鈀金屬錯合物催化Suzuki-Miyaura耦合反應
一、耦合反應簡介………………………………………………… 19
二、Suzuki-Miyaura耦合反應簡介……………………………… 20
三、有機及過渡金屬配位膦基…………………………………… 22
四、二級氧化膦基簡介…………………………………………… 26
五、研究方向……………………………………………………… 28
六、結果與討論…………………………………………………… 29
第一節 理論計算方法…………………………………………… 29
第二節 Suzuki-Miyaura耦合反應之催化循環………………… 30
第三節 以密度泛函數理論探討二茂鐵衍生膦基1,1’-dmpf、1,1’-dmpof與1,2-dmpf催化Suzuki-Miyaura耦合反應...31
第四節 以密度泛函數理論探討含鈷金屬之三明治化合物衍生膦基1,1’-dmpc,1,1’-dmpoc與1,2-dmpc催化Suzuki-Miyaura耦合反應…40
第五節 結論……………………………………………………… 46
七、參考文獻……………………………………………………… 47

Topic Part II 以含氮雜環碳烯-

1. Hohenberg, P.; Kohn, W. Phys. Rev.1964, 136, B864-B871.
2. Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133-A1138.
3. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio Molecular Orbital Theory; John Wiley & Sons: New York, 1986.
4. Lipkowitz, K. B., Boyd, D. B., Eds. Reviews in Computational Chemistry; VCH: New York, 1990-1999; Vols. 1-13.
5. (a) Koga, K.; Morokuma, K. Chem. Rev. 1991, 91, 823-842. (b) Musaev, D. G.; Morokuma, K. In Advances in Chemical Physics; Rice, S. A., Prigogine, I., Eds.; John Wiley & Sons: New York, 1996; Vol. XCV, p61. (c) Siegbahn, P. E. M.; Blomberg, M. R. A. In Theoretical Aspects of Homogeneous Catalysts, Application of Ab initio Molecular Orbital Theory; van Leeuwen, P. W. N. M., van Lenthe, J. H., Morokuma, K., Eds.; Kluwer Academic Publishers: Hingham, MA, 1995. (d) Ziegler, T. Chem. Rev. 1991, 91, 651. (e) Salahub, D. R.; Castro, M.; Fournier, R.; Calaminici, P.; Godbout, N.; Goursot, A.; Jamorski, C.; Kobayashi, H.; Martinez, A.; Papai, I.; Proynov, E.; Russo, N.; Sirois, S.; Ushio, J.; Vela, A. In Theoretical and Computational Approaches to Interface Phenomena; Sellers H., Olab, J., Eds.; Plenum Press: New York, 1995; p 187. (f) Siegbahn, P. E. M. In Advances in Chemical Physics; Rice, S. A., Prigogine, I., Eds.; John Wiley & Sons: New York, 1996; Vol. XCIII, p 333. (g) Transition Metal Hydrides, Edited by Dedieu, A., VCH Publishers: 1992. (h) Theoretical Aspects of Homogeneous Catalysts, Application of Ab initio Molecular Orbital Theory; van Leeuwen, P. W. N. M., van Lenthe, J. H., Morokuma, K., Eds.; The Netherlands, 1994. (i) Yoshida, S.; Sakaki, S.; Kobayashi, H. Electronic Processes in Catalyst; VCH: New York, 1992.
6. Levine, I. N. Quantum Chemistry, 4th ed., Prentice-Hall: New Jersey, 1991.
7. Gordon, M. H. J. Phys. Chem. 1996, 100, 13213-13225.
8. Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry, McGraw-Hill: New York, 1989.
9. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Wallingford CT, 2003.
10. Spartan ‘08; Wavefunction, Inc.: Irvine, CA. 2008.

Topic I.
1. General reviews, see (a) Cross-Coupling Reactions - A Practical Guide in Topics in Current Chemistry; Houk, K.N.; Sessler, H.; Lehn, J.-M.; Ley, S.V.; De Meijere, A.; Schreiber, S. L.; Thiem, J.; Trost, B. M.; V

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