臺灣博碩士論文加值系統

B. 含氟化合物之理論計算與碳-氘伸縮振動之探討
由於用X-ray繞射所得到的結構在鍵長上仍有較大的誤差值，所以用理論計算的方法，以密度泛函理論(DFT)的計算方式，計算出化合物之最佳化結構與振動光譜，並搭配IR圖譜中的實驗數據，配對出每一個訊號所代表的振動模式。同時也試著將含氟鏈吡啶上部分的氫原子以氘原子替換，透過觀察其位移狀況已幫助我們配對振動模式。

B. Calculations of Fluoro-containing Compounds and Research of Carbon-deuterium Stretching.
Since the structure obtained by X-ray diffraction has a bigger deviation on the bond length, the optimized structure of the compound is calculated by the method of density functional theory (DFT) using the theoretical calculation method. With the vibration spectrum, and with the IR spectrum of the experimental data, assigned each signal represents the vibration mode. We also tried to replace some of the hydrogen atom the fluorine-containing pyridine with a deuterium atom to help us assign the vibrational mode by considering the displacement of the signals.

目錄
摘 要 I
ABSTRACT II
誌謝 IV
目錄 V
表目錄 VII
圖目錄 VIII
(A) 新型短氟鏈吡啶及其反式鈀金屬鹵化物之結構 1
第一章 緒論 2
1-1前言 2
1-2文獻回顧 3
1-2-1 吡啶 3
1-2-2 鈀金屬錯合物 3
第二章 實驗方法 5
2-1研究藥品 5
2-2鑑定用儀器 8
2-2-1 霍式轉換核磁共振光譜儀 8
2-2-2 氣相色層分析串聯質譜儀(GC/MS)： 9
2-2-3 傅立葉轉換紅外線吸收光譜儀 9
2-2-4 真空減壓旋轉濃縮機(Rotary Evaporators) 9
2-2-5 水流抽氣機(Aspirator) 10
2-2-6 油迴轉式真空幫浦(Rotary Vacuum Pump) 10
2-3 實驗方法 11
2-3-1 3-(Bromomethyl)pyridine hydrobromide之合成 11
2-3-2 三取代含氟鏈吡啶之合成與處理 12
2-3-3 含氟吡啶鈀錯合物之合成 16
2-3-4再結晶(以(3-py-4FH)2PdBr2 為例) 34
第三章 結果與討論 35
3-1含氟鏈吡啶鈀金屬錯合物 35
3-2 晶體結構探討 36
3-2-1分子間作用力之探討 40
3-2-2以Gaussian理論計算修正晶體結構 41
3-2-3以理論計算搭配IR圖譜鑑定振動模式 42
第四章 結論 43
參考文獻 44
附錄 47
(B)含氟化合物之理論計算與碳-氘伸縮振動之探討 76
第一章 緒論 78
1-1前言 78
1-2文獻回顧 78
1-2-1 Gaussian計算軟體 78
1-2-2 藍位移氫鍵 79
1-2-3碳-氘伸縮振動 80
第二章 實驗方法 81
2-1研究藥品 81
2-2鑑定用儀器 84
2-2-1 霍式轉換核磁共振光譜儀 84
2-2-2 氣相色層分析串聯質譜儀(GC/MS)： 85
2-2-3 傅立葉轉換紅外線吸收光譜儀 85
2-2-4 真空減壓旋轉濃縮機(Rotary Evaporators) 85
2-2-5 水流抽氣機(Aspirator) 86
2-2-6 油迴轉式真空幫浦(Rotary Vacuum Pump) 86
2-3 實驗方法 87
2-3-1 3-pyridinemethanol-d2之合成 87
2-3-2 3-(Bromomethyl)pyridine hydrobromide-d2之合成 88
2-3-3合成3-4FH-py-d2氘代配位基 89
2-3-4氘代含氟吡啶鈀錯合物之合成 90
2-3-5 Gaussian 理論計算 92
第三章 結果與討論 93
3-1碳-氫與碳-氘伸縮振動之對照 93
3-1-1 3-(Bromomethyl)pyridine hydrobromide-d2 93
3-1-2 氘代含氟吡啶鈀錯合物 94
3-2 化學理論計算與振動光譜的配對 97
第四章 結論 102
參考文獻 103
附錄 107

(a)
1.Lu, Norman et al. "Molecularly Tuning The Radicaloid N–H···O═C Hydrogen Bond". The Journal of Physical Chemistry A 120.8 (2016): 1307-1315. Web.
2.K. Vinodhinia and K. Srinivasan*a The role of a mixture of DMSO : water in the crystallization of α-lactose monohydrate (α-LM) single crystals with desired morphology. CrystEngComm. 2015, 17, 6376-6383.
3.Lu, N., Lin, K., Kung, C., Jhuo, J., Zhou, Y., Liu, J., & Sun, L. (2014). Intercalated polyfluorinated Pd complexes in α-zirconium phosphate for Sonogashira and Heck reactions. RSC Advances, 4(52), 27329-27336
4.Seechurn, C., Kitching, M., Colacot, T., & Snieckus, V. (2012). ChemInform Abstract: Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize. Cheminform, 43(33), no-no.
5. Inagaki, S., Murai, H., & Takeuchi, T. (2012). Theory of electron localization and its application to blue-shifting hydrogen bonds. Physical Chemistry Chemical Physics, 14(6).
6.Se Ye Oh,a Christopher W. Nickels,b Felipe Garcia,c William Jones*a and Tomislav Frisˇcˇic´* "Switching Between Halogen- And Hydrogen-Bonding In Stoichiometric Variations Of A Cocrystal Of A Phosphine Oxide". CrystEngComm 14.19 (2012): 6110.
7.Li, C., Ghalwadkar, A., & Lu, N. (2011). Recoverable cationic Pd-catalyzed Heck reaction under thermomorphic mode. Journal of Organometallic Chemistry, 696(23), 3637-3642.
8.Norman Lu, Wen-Han Tu, Yuh-Sheng Wen, Ling-Kang Liu, Chun-Yi Chouc, Jyh-Chiang Jiang. The intramolecular blue-shifting C-H/F-C hydrogen bond: crystal structure of [4,4′ -bis(HCF2CF2CF2CF2CH2OCH2)-2,2′ -bpy]MCl2 where M ¼ Pt, Pd. CrystEngComm, 2010, 12, 538-542
9.Norman Lu, Wen-Han Tu, His-Chun Hou, Chien-Ting Lin, Chieh-Keng Li, Ling-Kang Liu. Synthesis, structure and spectroelectrochemical property of (2,2′-bipyridine)-metal (M = Pt, Pd) dichloride with 4,4′-bis(fluorous-ponytail) on -bipyridine.Polyhedron, 2010,29, 1123-1129
10.Stefano Libri, Naseralla A. Jasim, Robin N. Perutz, Lee Brammer, Metal Fluorides Form Strong Hydrogen Bonds and Halogen Bonds: Measuring Interaction Enthalpies and Entropies in Solution.J. AM. CHEM. SOC. 2008, 130, 7842-7844
11.Bakalova, Adriana et al. "Synthesis, Characterization And Biological Activity Of Pt(II) And Pt(IV) Complexes With 5-Methyl-5(4-Pyridyl)-2,4-Imidazolidenedione". European Journal of Medicinal Chemistry 43.5 (2008): 958-965.
12.Lu, N., Chen, S., Chen, T., & Liu, L. (2008). Palladium-catalyzed Heck reaction under thermomorphic mode. Tetrahedron Letters, 49(2), 371-375.
13.Norman Lu,* Yan-Chou Lin, Jeng-Yung Chen, Chi-Wen Fan, and Ling-Kang Liu;“ New Bis(fluoro-ponytailed) Bipyridine Ligands for Pd-catalyzed Heck Reactions under Fluorous Biphasic Catalysis Condition” Tetrahedron, 2007, 63, 2019-2023.
14.Jorly Joseph, Eluvathingal D. Jemmis, Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation. J. AM. CHEM, 2007, 129, 4620-4632
15.Barnes A.J, Blue-shifting hydrogen bonds—are they improper or proper? Journal of Molecular Structure, 2004, 704, 3-9
16.Kirsch, P.(2004). In Modern Fluoroorganic Chemistry: Synthesis,Reactivity, Applications. Weinheim: Wiley.
17.Pavel Hobza, Zdenek Havlas, Improper, blue-shifting hydrogen bond. Theor Chem Acc, 2002, 108, 325-334
18.Hermansson, Kersti. "Blue-Shifting Hydrogen Bonds". The Journal of Physical Chemistry A 106.18 (2002): 4695-4702.
19.Pavel Hobza, The H-index unambiguously discriminates between hydrogen bonding and improper blue-shifting hydrogen bonding.Chem. Phys., 2001, 3, 2555-2556
20.Pavel Hobza, Zdeneˇk Havlas, Blue-Shifting Hydrogen Bonds.Chem. Rev. 2000, 100, 4253-4264
21.Pavel Hobza*,†,‡ and Zdeneˇk Havlas‡,§. Blue-Shifting Hydrogen Bonds. Chem. Rev. 2000, 100, 4253-4264
22.Desiraju, G. R. & Steiner, T.(1999). The Weak Hydrogen Bonding in Structural Chemistry and Biology. Oxford University Press
23. Jeffrey, George A. An Introduction To Hydrogen Bonding. New York: Oxford University Press, 1997. Print.
24.O . HA S S E L, Structural aspects of interatomic charge-transfer bonding Nobel Lecture, 1970
25.黃家榆，末端含鹵素短氟鏈聯吡啶接上鈀、鉑金屬錯合物之相關研究，碩士論文，國立臺北科技大學有機高分子所，臺北，2016
26.魏榕均，新型含氟鏈吡啶鹽類及鈣鈦礦之合成與特性分析之研究，碩士論文，國立臺北科技大學有機高分子所，臺北，2016
27.鐘威丞，(a) 可回收含氟鉑金屬催化劑催化Hydrosilation之研究，(b) 新型含氟鉑金屬錯合物合成與鑑定，碩士論文，國立臺北科技大學有機高分子所，臺北，2014
28.卓均蔚，(a) 含短氟聯吡啶及其鈀和鉑錯合物之研究，(b) 含氟鏈鈀錯合物嵌入 ZrP 運用在Sonogashira 和Heck 反應，碩士論文，國立臺北科技大學有機高分子所，臺北，2013、(b)
1.Lu, N., Chung, W., Ley, R., Lin, K., Francisco, J., & Negishi, E. (2016). Molecularly Tuning the Radicaloid N–H···O═C Hydrogen Bond. The Journal Of Physical Chemistry A, 120(8), 1307-1315.
2.Abkari, A., Chaabane, I., & Guidara, K. (2016). DFT (B3LYP/LanL2DZ and B3LYP/6311G+(d,p)) comparative vibrational spectroscopic analysis of organic–inorganic compound bis(4-acetylanilinium) tetrachlorocuprate(II). Physica E: Low-Dimensional Systems And Nanostructures, 81, 136-144.
3.Karton, A. (2016). How reliable is DFT in predicting relative energies of polycyclic aromatic hydrocarbon isomers? comparison of functionals from different rungs of jacobs ladder. Journal Of Computational Chemistry, 38(6), 370-382.
4.Witte, J., Goldey, M., Neaton, J., & Head-Gordon, M. (2015). Beyond Energies: Geometries of Nonbonded Molecular Complexes as Metrics for Assessing Electronic Structure Approaches. Journal Of Chemical Theory And Computation, 11(4), 1481-1492.
5.Sousa, S., Pinto, G., Ribeiro, A., Coimbra, J., Fernandes, P., & Ramos, M. (2013). Comparative analysis of the performance of commonly available density functionals in the determination of geometrical parameters for copper complexes. Journal Of Computational Chemistry, 34(24), 2079-2090.
6.Kozuch, S., & Martin, J. (2013). Spin-component-scaled double hybrids: An extensive search for the best fifth-rung functionals blending DFT and perturbation theory. Journal Of Computational Chemistry, n/a-n/a.
7.Remya, K., & Suresh, C. (2013). Which density functional is close to CCSD accuracy to describe geometry and interaction energy of small noncovalent dimers? A benchmark study using Gaussian09. Journal Of Computational Chemistry, 34(15), 1341-1353.
8.
9.Goerigk, L., & Grimme, S. (2011). A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions. Physical Chemistry Chemical Physics, 13(14), 6670.
10.Luo, S., Zhao, Y., & Truhlar, D. (2011). Validation of electronic structure methods for isomerization reactions of large organic molecules. Physical Chemistry Chemical Physics, 13(30), 13683.
11.Yang, Y., Weaver, M., & Merz, K. (2009). Assessment of the “6-31+G** + LANL2DZ” Mixed Basis Set Coupled with Density Functional Theory Methods and the Effective Core Potential: Prediction of Heats of Formation and Ionization Potentials for First-Row-Transition-Metal Complexes. The Journal Of Physical Chemistry A, 113(36), 9843-9851.
12. Zandler, M., & DSouza, F. (2006). The Remarkable Ability of B3LYP/3-21G(*) Calculations to Describe Geometry, Spectral and Electrochemical Properties of Molecular and Supramolecular Porphyrin—Fullerene Conjugates. Cheminform, 37(50).
13.Perdew, J., Ruzsinszky, A., Tao, J., Staroverov, V., Scuseria, G., & Csonka, G. (2005). Prescription for the design and selection of density functional approximations: More constraint satisfaction with fewer fits. The Journal Of Chemical Physics, 123(6), 062201.
14.Bailey, W. (2000). DFT and HF–DFT calculations of quadrupole coupling constants in molecules. Chemical Physics, 252(1-2), 57-66.
15.French, A., Kelterer, A., Johnson, G., & Dowd, M. (2000). B3LYP/6-31G ∗ , RHF/6-31G ∗ and MM3 heats of formation of disaccharide analogs. Journal Of Molecular Structure, 556(1-3), 303-313.
16. Lotta, T., Murto, J., Räsänen, M., Aspiala, A., & Särkkä, P. (1985). Thermal and IR‐induced conformer interconversion processes for 2‐fluoroethylamine in several low‐temperature matrix media and ab initio 4‐31G, 4‐31G(N*), and 6‐31G** calculations. The Journal Of Chemical Physics, 82(3), 1363-1375.
17.Hobza, P., Szczȩśniak, M., & Latajka, Z. (1981). HF-ClF: minima on the 4-31G and 4-31G* energy hypersurfaces and thermodynamics of formation. Chemical Physics Letters, 82(3), 469-472.
18.魏榕均，新型含氟鏈吡啶鹽類及鈣鈦礦之合成與特性分析之研究，碩士論文，國立臺北科技大學有機高分子所，臺北，2016
19.Szabo, A., & Ostlund, N. (2006). Modern quantum chemistry. Mineola, N.Y.: Dover Publications.
20.D. Young. (2001). Computational Chemistry, A Practical Guide for Applying Techniques to Real World Problems, N.Y.: Wiley- Interscience .
21.J. Simmons. (2003) An Introduction to Theoretical Chemistry, Cambridge: Cambridge Press.
22.Leach, A. (2001). Molecular modelling. Harlow, England: Prentice Hall.
23.J. B. Foresman AND Æ. Frisch. (1996) Exploring Chemistry with Electronic Structure Methods, 2nd Editio, Pittsburgh: Gaussian, Inc., , PA.
24.Gaussian Error Messages - ACENET. Ace-net.ca. Retrieved July 2016, from https://www.ace-net.ca/wiki/Gaussian_Error_Messages
25.EMSL Basis Set Exchange. Retrieved July 2016, from https://bse.pnl.gov/bse/portal
26.Support | Gaussian.com. Gaussian.com. Retrieved July 2016, from http://gaussian.com/techsupport/