臺灣博碩士論文加值系統

氧化亞氮是工業上所排放的大量溫室氣體。因此，如何有效率的排除氧化亞氮將是一個饒富興趣的課題。去氮酵素氧化亞氮還原脢（denitrification enzyme nitrous oxide reductase (N2OR)），將N2O還原成N2及水，近來被發現是一個前所未有的[Cu4-µ4S]活化中心。儘管已經有許多已知的多核銅硫化合物，但是在N2O還原或是[Cu4-µ4S]的模型研究課題上卻鮮少有研究及報導。因此，四核橋接硫化合物[Cu4-µ4S]的合成將是N2OR活性中心的最佳模型，本實驗研究目的就是合成出四核橋接硫化合物的起始物：雙核橋接硫化合物[Cu2-µ2S]作為模型研究的基礎。

Nitrous oxide is a greenhouse gas produced in large quantity by several industrial processes. Efficient means of eliminating N2O are therefore of interest. The denitrification enzyme nitrous oxide reductase (N2OR), which reduces N2O to N2 and water , has recently been shown to contain an unprecedented [Cu4-µ4S] active site. Multinuclear copper sulfide compounds are known but have not been studied in the context of modeling N2OR or as N2O reduction catalysts. The synthesis of new tetranuclear [Cu4-µ4S] compounds is proposed to model the N2OR active site.The purpose of our research is to synthesize [Cu2-µ2S] complex, which original compound of [Cu4-µ4S] complex. This can be groundwork for mimicking the copper protein active site.

第壹章、 緒論…………………………………………………1
第貳章、 結果與討論
一、四氰甲烷銅一價錯合物與配位基 雙吡咯甲烷BPM
和三吡咯甲烷TPM反應性的探討……………...…..22
二、雙銅橋接硫化合物[Cu2-□2S]的合成及
反應性質………………………………………….....28
三、四氰甲烷銅一價錯合物與氰化鈉
反應性質的探討……………………..……………...35
四、雙銅橋接雙氮二芽基錯合物的合成
與反應性質的探討…………………………………...38
五、結論…………………………………………………...42
第叁章、 實驗部分
一、藥品來源及前處理……………………………………44
二、儀器部分………………………………………………47
三、實驗步驟……………………………………………….48
3.1 Cu(NCMe)4BF4 (1)的合成………..………………48
3.2 配位基Bis-(1-pyrazolyl)methane ( BPM )
的合成………………………….………………..49
3.3 配位基Tris(1-pyrazolyl)methane ( TPM )
的合成…………………………………………...50
3.4 Cu(BPM)(NCMe)nBF4的合成…………………....51
3.5 Cu(BPM)2BF4 (4)的合成……………………........52
3.6 Cu(TPM)(NCMe)BF4 (5)的合成………………....53
3.7 Cu(TPM)Cl (8)的合成…………………………....54
3.8 [ Cu(BPM)Cl ]n (9)的合成…..................................54
3.9 Cu(TPM)BF4 (5)與(TMS)2S的反應......................55
3.10 Cu(TPM)(NCMe)BF4 (5)與Na2S的反應…........56
3.11 Cu(TPM)Cl (8)與Na2S的反應….........................57
3.12 Cu(TPM)Cl (8)與(TMS)2S的反應…..................58
3.13 Cu(TPM)(NCMe)BF4 (5)與NaCN的反應…......60
3.14 Cu(TPM)(NCMe)BF4 (5)與pyrazine的反應…..60
3.15 Cu(TPM)(NCMe)BF4 (5)與4,4’-dipyridyl的反應.......................................................61
3.16 產物Cu(TPM)(Pyra)BF4 (13)與 Cu(TPM)(NCMe)BF4 (5)的反應……................62
3.17 Cu(TPM)CN (12)與Cu(TPM)(NCMe)BF4 (5)
的反應…………………………………………...63
參考文獻…………………………………………...65
附錄………………………………………………...67

(1)Su, C.-C.; Wu, C.-Y. Chemistry (The Chinese Chem. Soc.,Taipei) 1996, 54, 57.
(2)Kitajima, N. Adv. Inorg. Chem. 1992, 39, 1.
(3)Lippard, S. J.; Berg, J. M. Princuples of Bioinorganic Chemistry 1994, 115.
(4)Magnus, K. A.; Hoa, T.-T.; Carpenter, J. E. Chem. Rev. 1994, 94, 727-735.
(5)Solomon, E. I.; Tuczek, F.; Root, D. E.; Brown, C. A. Chem. Rev. 1994, 94, 827-856.
(6)Kitajima, N.; Moro-oka, Y. Chem. Rev. 1994, 94, 737-757.
(7)Karlin, K. D.; Kaderli, S.; Zuberbuhler, A. D. Acc. Chem. Res. 1997, 30, 139-147.
(8)Volbeda, A.; Hol, W. G. J. J. Mol. Biol. 1989, 209, 249-279.
(9)Henson, M. J.; Vance, M. A.; Zhang, C. X.; Liang, H.-C.; Karlin, K. D.; Solomon, E. I. J. Am. Chem. Soc. 2003, 125, 5186-5192.
(10)Kim, E.; Chufan, E. E.; Kamaraj, K.; Karlin, K. D. Chem. Rev. 2004, 104, 1077.
(11)Karlin, K. D.; Haka, M. S.; Cruse, R. W.; Gultneh, Y. J. Am. Chem. Soc. 1985, 107, 5828-5829.
(12)Liang, H.-C.; Karlin, K. D.; Dyson, R.; Kaderli, S.; Jung, B.; Zuberbuhler, A. D. Inorg. Chem. 2000, 39, 5884-5894.
(13)Schatz, M.; Becker, M.; Thaler, F.; Hampel, F.; Schindler, S.; Jacobson, R. R.; Tyeklar, Z.; Murthy, N. N.; Ghosh, P.; Chen, Q.; Zubieta, J.; Karlin, K. D. Inorg. Chem. 2001, 40, 2312-2322.
(14)Tyeklar, Z.; Jacobson, R. R.; Wei, N.; Murthy, N. N.; Zubieta, J.; Karlin, K. D. J. Am. Chem. Soc. 1993, 115, 2677-2689.
(15)Kodera, M.; Kajita, Y.; Tachi, Y.; Kano, K. Inorg. Chem. 2003, 42, 1193-1203.
(16)Mahapatra, S.; Halfen, J. A.; Wilkinson, E. C.; Pan, G.; Wang, X.; Young, V. G., Jr.; Cramer, C. J.; Que, L., Jr.; Tolman, W. B. J. Am. Chem. Soc. 1996, 118, 11555-11574.
(17)Lam, B. M. T.; Halfen, J. A.; Young, V. G., Jr.; Hagadorn, J. R.; Holland, P. L.; Lledos, A.; Cucurull-Sanchez, L.; Novoa, J. J.; Alvarez, S.; Tolman, W. B. Inorg. Chem. 2000, 39, 4059-4072.
(18)Lewis, E. A.; Tolman, W. B. Chem. Rev. 2004, 104, 1047-1076.
(19)Holland, P. L.; Tolman, W. B. Coor. Chem. Rev. 1999, 190-192, 855-869.
(20)Tolman, W. B. Acc. Chem. Res. 1997, 30, 227-237.
(21)Zumft, W. G. Microbiology & Molecular Biology Reviews 1997, 61.
(22)Rasmussen, T.; Berks, B. C.; Sanders-Loehr, J.; Dooley, D. M.; Zumft, W. G.; Thomson, A. J. Biochemistry 2000, 39, 12753-12756.
(23)Prudencio, M.; Pereira, A. S.; Tavares, P.; Besson, S.; Cabrito, I.; Brown, K.; Samyn, B.; Devreese, B.; Van Beeumen, J.; Rusnak, F.; Fauque, G.; Moura, J. J. G.; Tegoni, M.; Cambillau, C.; Moura, I. Biochemistry 2000, 39, 3899-3907.
(24)Helton, M. E.; Chen, P.; Paul, P. P.; Tyeklar, Z.; Sommer, R. D.; Zakharov, L. N.; Rheingold, A. L.; Solomon, E. I.; Karlin, K. D. J. Am. Chem. Soc. 2003, 125, 1160-1161.
(25)Houser, R. P.; Halfen, J. A.; Young, V. G., Jr.; Blackburn, N. J.; Tolman, W. B. J. Am. Chem. Soc. 1995, 117, 10745-10746.
(26)Halfen, J. A.; Young, V. G., Jr.; Tolman, W. B. J. Am. Chem. Soc. 1996, 118, 10920-10921.
(27)Itoh, S.; Nagagawa, M.; Fukuzumi, S. J. Am. Chem. Soc. 2001, 123, 4087-4088.
(28)Brown, E. C.; Aboelella, N. W.; Reynolds, A. M.; Aullon, G.; Alvarez, S.; Tolman, W. B. Inorg. Chem. 2004, 43, 3335-3337.
(29)Yam, V. W.-W.; Lee, W.-K.; Lai, T.-F. Chem. Commun. 1993, 1571-1573.
(30)Jameson, D. L.; Castellano, R. K.; Reger, D. L.; Collins, J. E.; Tolman, W. B.; Tokar, C. J. Inorg. Syn. 1998, 32, 51-63.
(31)Trofimenko, S. Chem. Rev. 1993, 93, 943-980.
(32)De Bari, H.; Zimmer, M. Inorg. Chem. 2004, 43, 3344-3348.
(33)Cvetkovic, M.; Batten, S. R.; Moubaraki, B.; Murray, K. S.; Spiccia, L. Inorganica Chimica Acta 2001, 324, 131-140.
(34)Reger, D. L.; Collins, J. E.; Rheingold, A. L.; Liable-Sands, L. M. Organometallics 1996, 15, 2029-2032.
(35)Lim, B. S.; Holm, R. H. Inorg. Chem. 1998, 37, 4898-4908.