以實驗室先前合成的P(C6H3-3-SiMe3-2-S)3能產生出一系列鎳三價
錯合物為想法出發，改合成出P(C6H4-2-N(CH3)2)3，期許能以其產生出鎳一價錯合物，並研究其對小分子的活化。
將NiII(ClO4)2•6H2O等比例加入P(C6H4-2-N(CH3)2)3並溶於MeCN中，於室溫、氮氣環境下可以得到[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1)，利用X-ray單晶繞射解析、超導量子干涉儀、電子順磁共振光譜儀、核磁共振儀、IR光譜儀和UV-Vis光譜儀鑑定錯合物1，可知鎳金屬為正二價high-spin且含兩個未成對電子，六配位扭曲的八面體結構。此外，可改用Ni粉及[NO][BF4]溶於MeCN中，合成出[Ni(NCMe)6][BF4]2，再與等比例的P(C6H4-2-N(CH3)2)3反應後得到[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2)，來達成改變陰離子的目的。
將錯合物1或2與當量的KC8於低溫、氮氣下的環境反應可以生成[NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X = ClO4或BF4) (3)，利用UV-Vis與EPR光譜可以測得錯合物3的訊號，發現錯合物3對氧氣敏感，並推測其Ni中心金屬只與ligand上之P原子及兩個solvent (-NCCH3)的氮原子有配位，形成扭曲平面三角形結構。在活化小分子方面，錯合物3可和CS2、CO2反應，推測會產生[NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)]及[NiIII(η2-CO2)(P(C6H4-2-N(CH3)2)3)]，由UV-Vis光譜及EPR來鑑定產物。
將[NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)]加入等當量的KC8於低溫、氮氣下反應，得到[NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4)，利用X-ray、UV-Vis、IR、1H NMR鑑定錯合物4的鎳金屬為正二價low-spin，四配位扭曲的平面四邊形結構。

The previously synthesized P(C6H3-3-SiMe3-2-S)3 can serve as a ligand to produce a series of nickel(III) complexes.Here we synthesize P(C6H4-2-N(CH3)2)3, expected to produce Ni(I) complex, and study its effect on the activation of small molecules.
The NiII(ClO4)2 • 6H2O reacting with P(C6H4-2-N(CH3)2)3 (1:1 molar ratio) in MeCN at room temperature under dinitrogen atmosphere yielded complex [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)] [ClO4]2 (1). Complex 1, characterized by single-crystal X-ray diffraction, SQUID, EPR, 1H NMR, IR and UV-Vis, was demonstrated to be mononuclear high-spin Ni(II) complex, containing two unpaired electrons. The geometry of the Ni center is a six-coordinate distorted octahedral complex. In addition, Ni powder and [NO][BF4] were reacted to synthesize [Ni(NCMe)6][BF4]2. Reaction of [Ni(NCMe)6][BF4]2 with an equal proportion of P(C6H4-2-N(CH3)2)3 yielded complex [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2).
Complexes 1 or 2 reacting with the equivalent of KC8 at low temperatures under dinitrogen atmosphere, respectively, yielded complex [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X = ClO4or BF4) (3). Complex 3 was sensitive to dioxygen and was characterized by UV-Vis and EPR spectroscopy. In the activation of small molecules, compound 3 may react with CS2 or CO2, to yield [NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] or [NiIII(η2-CO2)(P(C6H4-2-N(CH3)2)3)], characterized by UV-Vis and EPR.
The [NiIII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] reacting with KC8 in 1:1 molar ratio at low temperatures under dinitrogen atmosphere produced [NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4). Complex 4, characterized by X-ray, UV-Vis, IR, 1H NMR, was low-spin Ni(II) complex.The geometry of the Ni center is a four-coordinate distorted square-planar complex.

目錄
第一章、緒論 9
1-1 前言 9
1-2 二氧化碳(CO2)之性質 10
1-2-1 分子幾何 10
1-2-2 光譜性質 12
1-2-2-1 Infrared(IR) 12
1-2-2-2 UV-Vis 12
1-2-2-3 13C-Nuclear Magnetic Resonance(NMR) 12
1-2-3 物理、化學性質與安全性 13
1-3 CO2與金屬中心的配位及反應 14
1-3-1 配位模式 14
1-3-2 CO2配位過渡金屬系統之反應性 15
1-4 鎳(Nickel)為中心之活化CO2的研究 17
1-5 鎳(Nickel)為中心之活化二氧化硫(CS2)的研究 19
1-6 研究方向 24
第二章、實驗部分 25
2-1 一般實驗 25
2-2 儀器 26
2-3 藥品 27
2-4 Ligand的合成 28
2-5 錯合物的合成及鑑定 30
1. 合成[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1) 30
2. 合成[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2) 30
3. 合成[NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3) 31
4. 合成[NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4) 32
2-6錯合物的反應 33
1. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與O2/CO/N2O/CO2的反應 33
2. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與CS2的反應 33
3. [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2與KO2的反應 33
4. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) 與O2的反應 34
5. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CO / N2O的反應 34
6. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CS2的反應 35
7. [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] 與CO2的反應 35
2-7 晶體結構解析(Crystallography) 37
第三章、結果與討論 40
3-1 P(C6H4-2-N(CH3)2)3的合成、結構和光譜分析 40
3-2 [NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][ClO4]2 (1) 與[NiII(NCMe)2(OH2)(P(C6H4-2-N(CH3)2)3)][BF4]2 (2) 的合成、結構和光譜分析 42
3-3 [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3)的合成與光譜分析 51
3-4 [NiI(NCMe)2(P(C6H4-2-N(CH3)2)3)][X] (X=BF4 or ClO4) (3)與CS2、CO2的反應 56
3-5 [NiII(η2-CS2)(P(C6H4-2-N(CH3)2)3)] (4) 的合成、結構和光譜分析 60
第四章、結論 68
Reference 70

1. (a) The first report was by Bassarov in 1870, see Fromm, D.; Lutzov, D. Chem. Uns. Zeit. 1979, 13, 78. (b) Kolbe, H.;Lautemann, E. Ann. 1869, 113, 125. (c) Schmitt, R.; Burkard, E. Ber. 1877, 20, 2699.
2. Allam, R. J.;Bredesen,R.; Drioli,E. in Carbon Dioxide Recovery and Utilization, 2003, pp. 53–118.
3. (a) Mathisen, A. in Proc ICCDU VIII, June 20–23, 2005, p. 2. (b) Kongsjordan, H.; Karstad, O.; Torp, T. A. Waste Manag 1997, 17, 303–308.
4. Simone, J. De. in Proc ICCDU VI, September 9–14, 2001, p. 33.
5. Vansant, J. in Recovery and Utilization of Carbon Dioxide, M. Aresta (Ed.), Kluwer, Dordrecht, 2003, pp. 3–50.
6. Aresta, M.; Dibenedetto, A. in CO2 Conversionand Utilization, ACS Symp. Ser. 809, C. Song, Gaffney, A. M.; Fujimoto, K. (Eds.), ACS, Washington, DC, 2002, pp. 54-70.7.
7. Rabalais, J. W.; McDonald, J. M.; Scherr, V.; McGlynn, S. P. Chem. Rev. 1971, 71, 73-108 and references therein.
8. Shemansky, D. E. J. Chem. Phys. 1972, 56, 1582–1587.
9. Liger-Belair, G.; Prost, E.; Parmentier, M.; Jeandet, P.; Nuzillard, J.-M. Agric Food Chem. 2003, 51, 7560–7563.
10. Gibson, D. H. Chem. Rev. 1996, 96, 2063–2095.
11. (a) Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 2391–2392. (b) Calabrese, J. C.; Herskovitz, T.; Kinney, J. B. J. Am. Chem. Soc. 1983, 105, 5914–5915.
12. Castro-Rodriguez, I.; Nakai, H.; Zakharov, L.; Rheingold, A. L.; Meyer, K. Science 2004, 305, 1757–1759.
13. (a) Aresta, M.; Nobile, C. F. Dalton Trans 1977, 7, 708–711. (b) Mason, M. G.; Ibers, J. A. J. Am. Chem. Soc. 1982, 104, 5153–5157. (c) Doehring, A.; Jolly, P. W.; Krueger, C.; Romao, M. Z Natur forsch 1985, 40B, 484–488.
14. (a) Aresta, M.; Nobile, C. F. Inorg. Chim. Acta 1977, 24, L49–L50. (b) Aresta, M.; Quaranta, E.; Tommasi, I. New J. Chem. 1994, 18, 133–142.
15. (a) Karsch, H. H. Chem. Ber. 1977, 110,2213. (b) Komiya, S.; Akita, M.; Kasuga, N.; Hirano, M.; Fukuoka, A. Chem. Commun. 1994, 9, 1115–1116.
16. Sakamoto, M.; Shimizu, L.; Yamamoto, A. Organometallics 1994, 13, 407–409.
17. (a) Tetrick, S. M.; Thom, F. S.; Cutler, A. R. J. Am. Chem. Soc. 1998, 119, 6193–6194.(b) Tetrick, S. M.; Xu, C.; Pinkes, J. R.; Cutler, A. R. Organometallics 1998, 17, 1861–1867.
18. Hanna, T. A.; Baranger, A. M.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 3292–3293.
19. Audett, J. D.; Collins, T. J.; Santarsiero, B. D.; Spies, G.H. J. Am. Chem. Soc. 1982, 104, 7352–7353.
20. Kubiak, C. P.; Woodcock, C.; Eisenberg, R. Inorg. Chem. 1982, 21, 2119–2126.
21. (a) Field, J. S.; Haines, R. J.; Sundermeyer, J.; Woollam, S. F. Chem. Commun. 1990, 14, 985–988. (b) Field, J. S.; Haines, R. J.; Sundermeyer, J.; Woollam, S. F. Dalton Trans. 1993, 18, 2735–2748.
22. Tso, C. T.; Cutler, A. R. J. Am. Chem. Soc. 1986, 108, 6069.
23. (a) Vites, J. C.; Steffey, B. D.; Giuseppetti-Dery, M. E.; Cutler, A. R. Organometallics 1991, 10, 2827–2834. (b) Pinkes, J. R.; Steffey, B. D.; Vites, J. C.; Cutler, A. R. Organometallics 1994, 13, 21–23.
24. Senn, D. R.; Gladysz, J. A.; Emerson, K.; Larsen, R. D. Inorg. Chem. 1987, 26, 2737–2739.
25. Gibson, D. H.; Ye, M.; Sleadd, B. A.; Mehta, J. M.; Mbadike, O. P.; Richardson, J. F.; Mashuta, M. S. Organometallics 1995, 14, 1242–1255.
26. (a) Eady, C. R.; Guy, J. J.; Johnson, B. F. G.; Lewis, J.; Malatesta, M. C.; Sheldrick, G. M. Chem. Commun. 1976, 602. (b) John, G. R.;Johnson, B. F. G.; Lewis, J.; Wong, K. C. J. Organomet. Chem. 1979, 169, C23.
27. Balbach, B. K.; Helus, F.; Oberdorfer, F.; Ziegler, M. L. Angew Chem. 1981, 93, 479–480.
28. (a) Floriani, C.; Fachinetti, G. Chem. Commun.1974, 15, 615–616. (b) Fachinetti, G.; Floriani, C.; Zanazzi, P. F. J. Am. Chem.Soc. 1978, 100, 7405–7407. (c) Gambarotta, S.; Arena, F.; Floriani, C.; Zanazzi, P. F. J. Am. Chem. Soc. 1982, 104, 5082–5092.
29. (a) Gibson, D. H. Coord. Chem. Rev. 1999, 185–186, 335–355. (b) Gibson, D. H. Comp. Coord. Chem. II 2004, 1, 595–602.
30. (a) Aresta, M.; Quaranta, E.; Tommasi, I. Chem. Commun. 1988, 7, 450–452.(b) Tanaka, K.; Ooyama, D. Coord. Chem.Rev. 2002, 226, 211–218.
31. Yoshida, T.; Thorn, D.; Okano, T.; Ibers, J. A.; Yamamoto, A. J. Am. Chem. Soc. 1979, 101, 4212–4221.
32. Calabrese, J. C.; Herskovitz, T.; Kinney, J. B. J. Am. Chem. Soc. 1983, 105, 5914–5915.
33. Tsai, J.-C.; Khan, M.; Nicholas, K. M. Organometallics 1989, 8, 2967–2970.
34. (a) Demerseman, B.; Bouquet, G.; Bigorgne, M. J. Organomet. Chem. 1978, 145, 41–48. (b) Felkin, H.; Knowles, P. J.; Meunier, B.J. Organomet. Chem. 1978, 146, 151–153.
35. Aresta, M.; Nobile, C. F.; Albano, V. G.; Forni, E.; Manassero, M. Chem. Commun. 1975, 15, 636–637.
36. (a) Nicholas, K. M. J. Organomet. Chem. 1980, 188, C10–C12. (b) Bianchini, C.; Meli, A.J. Am. Chem. Soc. 1984, 106, 2698–2699.
37. (a) Tsuda, T.; Sanada, S. I.; Saegusa, T. J. Organomet. Chem. 1976, 116, C10–C12. (b) Delact, D. L.; Rosario, R. Del.; Fanwick, P. E.; Kubiak, C. P. J. Am. Chem. Soc. 1987, 109, 754–755. (c) Wu, J.; Fanwick, P. E.; Kubiak, C. P. Organometallics 1987, 6, 1805–1807.
38. (a) Chatt, J.; Kubota, M.; Leigh, G.-J.; March, F. C.; Mason, R.; Yarrow, D. J. Chem. Commun. 1974, 24, 1033–1034. (b) Karsch, H. H. Chem. Ber. 1977, 110, 2213. (c) Fachinetti, G.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. J. Am. Chem. Soc. 1979, 101, 1767–1775. (d) Burkhart, C.; Hoberg, H. Angew Chem. Int. Ed. 1982, 21, 76. (e) Bianchini, C.; Mealli, C.; Meli, A.; Sabat, M. Inorg. Chem. 1984, 23, 2731–2732. (f) Fachinetti, G.; Fochi, G.; Funaioli, T.; Zanassi, P. F. Chem. Commun. 1987, 2, 89–90. (g) Lee, G. R.; Maher, J. M.; Cooper, N. J. J. Am. Chem. Soc. 1987, 109, 2956–2962. (h) Belmore, K. A.; Vanderpool, R. A.; Tsai, J.-C.; Kahn, M. A.; Nicholas, K. M. J. Am. Chem. Soc. 1988, 110, 2004–2005. (i) Ruiz, J.; Guerchis, V.; Astrc, D. Chem. Commun. 1989, 812.
39. Aresta, M.; Nobile, C. F. Chem. Commun. 1975, 466, 636-637.
40. Anderson, J. S.; Iluc, V. M.; Hillhouse, G. L. Inorg. Chem. 2010, 49, 10203-10207.
41. Baird, M.; Hartwell, G.; Mason, JR. R.; Rae, A. I. M.; Willkinson, G. Chem. Commun. 1967, 988, 92-94.
42. Bheemaraju, A.; Beattie, J. W.; Lord, R. L.; Martin, P. D.; Groysman, S. Chem. Commun. 2012, 48, 9595-9597.
43. Telser, J.; Braz, J. Chem. Soc. 2010, 21, 1139–1157.
44. (a) Page, M. J.; Lu, W.-Y.; Poulten, R. C.; Carter, E.; Algarra, A. G.; Kariuki, B. M.; Macgregor, S. A.; Mahon, M. F.; Cavell, K. J.; Murphy, D. M.; Whittlesey, M. K. Chem. Eur. J. 2013, 19, 2158–2167. (b) Saraev, V. V.; Kraikivskii, P. B.; Lazarev, P. G.; Myagmarsuren, G.; Tkach, V. S.; Schmidt, F. K.; Russ. J. Coord. Chem. 1996, 22, 615–621. (c) Saraev, V. V.; Kraikivskii, P. B.; Svoboda, I.; Kuzakov, A. S.; Jordan, R. F. J. Phys. Chem. A 2008, 112, 12449–12455. (d) Nilges, M. J.; Barefield, E. K.; Belford, R. L.; Davies, P. H. J. Am.Chem. Soc. 1977, 99, 755–760.