臺灣博碩士論文加值系統

這篇論文包含了實驗與計算化學.分別為:新型態含鈷有機金屬磷基之設計、合成與催化應用及密度泛函數理論計算於雙鈷媒介合成尿素衍生物之反應機構研究.
我們已經發展出了一系列含鈷金屬的雙牙與單牙磷基.在雙牙磷基部份成功合成出了幾種與金屬不同配位模式之化合物;在單牙磷基方面,我們也成功的應用於Suzuki-Miyaura耦合反應並根據31P NMR與DFT計算提出了可能的催化活性中心.
在計算化學方面,我們用密度泛函數理論計算雙鈷媒介合成尿素衍生物的反應機構.除了提出可能的反應機構外,根據計算也預測了一種實驗尚未鑑定出來的產物.

This Ph. D thesis comprises two distinct parts which are Experiment (PART I: Design, Synthesis, Catalytic Application of a Novel Dicobalt Carbonyl-Containing Phosphine Family) and Computation (PART II: Density Functional Studies on Dicobalt- Octacarbonyl Mediated Urea Formation from Primary Amine) studies in the field of Chemistry.
In Part I, several dicoblat-containing di-phosphine Ligand [{μ-P,P-PPh2CH2PPh2}Co2(CO)4{μ-PPh2CCPPh2}] (3-1)-chelated metal complexes were prepared and their fluxional behavior of the bridging DPPM on complexes were examined by variable- temperature NMR experiments. Moreover, a novel dicobalt-containing mono-phosphine ligand, [(μ-PPh2CH2PPh2)Co2(CO)4][μ-PhCCP(t-Bu)2] 4a, was synthesized and characterized. The applications of this newly-made ligand in the Suzuki-Miyaura reactions were pursued and results were encouraging. A 31P NMR study of the reaction of 4a with Pd(OAc)2 reveals the significant reductive ability of 4a toward Pd(II). Two potential active species I and II involved in the catalytic reaction are proposed and subjected to DFT studies. Based on the 31P NMR and DFT studies, the processes of the generation of plausible active species for the Suzuki-Miyaura reactions are presented.
In Part II, two alternatively reaction pathways, Route 1 and 2, are proposed and examined for the Co2(CO)8 mediated urea formation of primary amine, NH2CH3, utilizing density functional theory method. The hydride migration process is found as the rate-determining step, while a formaide derivative is predicted as a potential product as well.

PART I: Design, Synthesis, Catalytic Application of a Novel Dicobalt Carbonyl-Containing Phosphine Family
Charpter 1_Introduction
Transition-metal phosphine family 1
1.1 Transition-metal phosphine families: features and
application 2
2.2 Alkyne-bridged dicobalt carbonyl backbone TM-phosphines: our previous studies 8
Charpter 2_Introduction
Suzuki-Miyaura cross-coupling reaction 13
2.1 Cross-coupling reactions 14
2.2 Catalytic cycleof Suzuki-Miyaura reaction 19
2.3 Elementary ingredients of Suzuki-Miyaura reaction 22
Charpter 3_Results and Discussion
Coblat-containing Di-phosphine Ligand 31
3.1 Synthesis of dicoblat-containing di-phosphine
Ligand 32
3.2 Fluxional behavior of dppm in dicoblat-containing
di-phosphine Ligand 43
3.3 Experimental Section 50
Charpter 4_Results and Discussion
Coblat-containing Mono-phosphine Ligands 59
4.1 Synthesis of dicoblat-containing mono-phosphine
Ligand 61
4.2 Application to Suzuki-Miyaura cross-coupling
reaction 71
4.3 31P NMR studies on 4a and 4a/Pd(OAc)2 77
4.4 Computational studies of the active species Ia, [Ia-OAc]-
and Ib 89 4.5 Experimental Section 92
PART II: Density Functional Studies on Dicobalt- Octacarbonyl Mediated Urea Formation from Primary Amine
Charpter 5_Introduction
Computational transition metal chemistry 125
5.1 Brief explanation of density functional theory 126
5.2 The employment of pseudopotintial basis sets in
transition metal systems 133
Charpter 6_Results and Discussion
Density Functional Studies on Dicobalt Octacarbonyl Mediated
Urea Formation from Primary Amine 137
6.1 General introduction to this subject 138
6.2 Computational Methods 141
6.3 An Insertion-Addition Pathway 143
6.4 An Addition-Insertion Pathway 157
6.5 Concluding Remarks 170
Charpter 7_ Supporting Information 175
7.1 Optimized Geometries and energies of the
Insertion-Addition pathway at B3LYP/631LAN
level of theory 176
7.2 Optimized Geometries and energies of the
Addition-Insertion pathway at B3LYP/631LAN
level of theory 192
Publication List 207
Appendix I
Tables of X-Ray Studies
1. [{μ-P,P-PPh2CH2PPh2}Co2(CO)4{μ-P,P-PPh2CCPPh2} Mo(CO)4], [(3-1)-Mo(CO)4] 3-4 (Chapter3) 211
2. [{μ-P,P-PPh2CH2PPh2}Co2(CO)4{μ-P,P-PPh2CCPPh2}W(CO)4], [(3-1)-W(CO)4] 3-5 (Chapter3) 218
3. [(μ-Ph2PCH2PPh2)Co2(CO)4][(μ-P,P-Ph2PCCPPh2)-Ru3(CO)10], [(μ-(3-1))-Ru3(CO)10] 3-6 (Chapter3) 225
4. [{μ-P,P-PPh2CH2PPh2}Co2(CO)4]{P-PPh2CCP(=O)Ph2}Fe(CO)5, [(3-2)-Fe(CO)4] 3-8 (Chapter3) 233
5. (μ-PPh2CH2PPh2)Co2(CO)6, 3 (Chapter4) 240
6. [(μ-PPh2CH2PPh2)Co2(CO)4][μ,η-PhCCP(t-Bu)2],
4b (Chapter4) 245

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1. (a) Suzuki, A. in Metal-Catalyzed Cross-coupling Reactions; Diederich, F.; Stang, P. J., Eds.; Wiley-VCH, Weinheim, Germany, 1998, Chapter 2. (b) Miyura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. (c) Suzuki, A. J. Organomet. Chem. 1999, 576, 147.
2. General reviews, see (a) Cross-Coupling Reactions - A Practical Guide in Topics in Current Chemistry; Houk, K.N., Kessler, H., Lehn, J.-M., Ley, S.V., Meijere, A.d., Schreiber, S.L., Thiem, J., Trost, B.M., Vögtle, F., Yamamoto, H., Eds.; Springer-Verlag Heidelberg, 2002; Vol. 219. (b) Hegedus, L. S. in Organometallics in Organic Synthesis; Schlosser, M. Eds.; Wiley, New York, 1994; p 383. (c) Palladium Reagents and Catalysts: Innovations in Organic Synthesis, Tuji, J., Eds., Wiley, Chichester, 1995. (d) Geissler, H. in Transition Metals for Organic Synthesis; Beller, M.; Bolm, C., Eds., Wiley-VCH,Weinheim, 1998, Vol 1, pp 158—193. (e) Metal-Catalyzed Cross-coupling Reactions; Diederich, F.; Stang, P. J., Eds.; Wiley-VCH, Weinheim, Germany, 1998 (f) Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist, Li, J. J., Gribble, G. W., Eds., Pergamon, Amsterdam, 2000.
3. (a) Chemler, S. R.; Trauner, D.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2001, 40, 4544. (b) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; J. Yin, Buchwald, S. L. J. Org. Chem. 2000, 65, 1158. (c) Wolfe, J. P.; Buchwald, S. L. Angew. Chem. Int. Ed. 1999, 38, 2413. (d) Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 9550. (e) Bei, X.; Crevier, T.; Guram, A. S.; Jandeleit, B.; Powers, T. S.; Turner, H. W.; Uno, T.; Weinberg, W. H. Tetrahedron Lett. 1999, 40, 3855. (f) Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 1998, 37, 3387.
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