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| 研究生： |
張凱傑 Chang, Kai-Chieh |
|---|---|
| 論文名稱： |
Synthesis and Reactivity of V2, Co2 and Ni2 Complexes 雙核釩、鈷、鎳錯合物的合成與化性研究 |
| 指導教授： |
蔡易州
Tsai, Yi-Chou |
| 口試委員: | |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2009 |
| 畢業學年度： | 97 |
| 語文別： | 中文 |
| 論文頁數： | 117 |
| 中文關鍵詞： | 雙核 、雙核鎳 、雙核鈷 、雙核釩 |
| 相關次數： | 點閱：1 下載：0 |
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將(Nacnac)DippCo(μ-Cl)2Li(THF)2 (Nacnac = HC(C(Me)NC6H3iPr2)2)在甲苯中利用KC8還原，可以成功的分離得到反三明治式雙核鈷錯合物－(μ-η2:η2-C7H8)[Co(Nacnac)Dipp]2 (1)，我們發現錯合物1對於小分子以及有機化合物皆有很好的反應性，產生許多新奇的鈷錯合物。利用1與白磷反應會得到以四個磷原子橋接的(μ-η4:η4-P4)[Co(Nacnac)Dipp]2 (2)，若再將2於100 ℃加熱四天，則會失去一個磷原子而產生(μ-η3:η3-P3)[Co(Nacnac)Dipp]2 (3)。另外利用1加入十六族元素後分別可分離得到[Co(Nacnac)Dipp(μ-X)]2 (4: X = S; 5: X = Se)與[Co(Nacnac)Dipp(μ-TeH)]2 (6)。而通入過量的一氧化氮則會得到逆磁性的Co(Nacnac)Dipp(NO)2 (7)。接著利用錯合物1和有機分子反應：加入對位疊氮甲苯後除了得到五員環單核的Co(Nacnac)Dipp(1,4-p-Tol2N4) (8)外，亦可分離出另一含量較少的雙核產物[Co(Nacnac)Dipp(μ-N-p-Tol)]2 (9)。和偶氮苯反應會得到將氮-氮雙鍵輕微活化的(μ-κ1:κ1-PhNNPh)[Co(Nacnac)Dipp]2 (10)。除此之外，1亦能催化末端炔類進行三聚合環化反應；而與立體阻礙較大的炔類如三甲基矽乙炔反應，則會生成三鍵配位於鈷上的錯合物－Co(Nacnac)Dipp(η2-Me3SiCCH) (12)。和1,3,5,7-環辛四烯反應會得到文獻上罕見的C16H16Co2(Nacnac)Dipp2 (13)，其中環辛四烯二聚合形成七六七的融合環連接兩個鈷；但加入1,3,5-環庚三烯卻得到把橋接的甲苯分子取代的錯合物－(μ-η4:η4-C7H8)[Co(Nacnac)Dipp]2 (14)。
除此之外，我們使用立體阻礙較小的配基與釩反應得到(Nacnac)ArVCl2 (Ar = Dmp or Dep)，接著再以四氫呋喃為溶劑在氮氣環境下還原，卻得到沒有固定氮氣的錯合物－[(Nacnac)ArV]2 (15: Ar = Dmp; 16: Ar = Dep)。
另一方面，利用amidinate配基與無水的氯化亞鈷和碘化鎳反應分別得到(DippNC(H)NDipp)Co(μ-Cl)2Li(THF)2 (18)和(η1-DippNC(H)NDipp)NiI3Li(THF)2(OEt2)2 (22)，分別將其還原可分離出無前例低配位的雙核錯合物－[M(μ-η2-DippNC(H)NDipp)]2 (20: M = Co; 24: M = Ni)。除此之外若利用22加入1.5當量的還原劑，則可分離得到(μ-I)[Ni(μ-η2-DippNC(H)NDipp)]2 (23)。
Reduction of (Nacnac)DippCo(μ-Cl)2Li(THF)2 (Nacnac = HC(C(Me)NC6H3iPr2)2) by KC8 in toluene led to isolation of inverted-sandwich complex (μ-η2:η2-C7H8)[Co(Nacnac)Dipp]2 (1) in good yield. Then we found compound 1 able to activate small molecules and various organic functionalities, generating novel cobalt-containing complexes. Treatment of 1 with P4 afforded a P4-bridged compound (μ-η4:η4-P4)[Co(Nacnac)Dipp]2 (2), then we heat 2 for 4 days resulted in (μ-η3:η3-P3)[Co(Nacnac)Dipp]2 (3) with one phosphorus loss. Reaction with chalcogen elements furnished [Co(Nacnac)Dipp(μ-X)]2 (4: X = S; 5: X = Se) and [Co(Nacnac)Dipp(μ-TeH)]2 (6) respectively. While treatment of 1 with excess nitric oxide afforded diamagnetic compound Co(Nacnac)Dipp(NO)2 (7). Then we investigated the reactivity of 1 with organic functionalities. Reaction with p-TolN3 produced not only a five-membered-ring complex Co(Nacnac)Dipp(1,4-p-Tol2N4) (8), but a minor product [Co(Nacnac)Dipp(μ-N-p-Tol)]2 (9). Treatment of 1 with azobenzene led to isolation of (μ-κ1:κ1-PhNNPh)[Co(Nacnac)Dipp]2 (10), which had slightly activated N-N bond. Moreover, complex 1 can catalyze cyclotrimerization of alkynes and form C-C triple bond coordinated complexes while reaction with more steric hindered alkynes such as Me3SiCCH. The reaction of 1 with 1,3,5,7-cyclooctatetraene afforded novel compound C16H16Co2(Nacnac)Dipp2 (13), two COTs forming a new C16H16 skeleton containing 3 fused ring. While treatment with 1,3,5-cycloheptatiene produced (μ-η4:η4-C7H8)[Co(Nacnac)Dipp]2 (14) without dimerization of cycloheptatriene.
Moreover, we used less hindered ligand to synthesize vanadium complex (Nacnac)ArVCl2 (Ar = Dmp or Dep). Then we reduced it by KC8 in THF under N2 afforded [(Nacnac)ArV]2 (15: Ar = Dmp; 16: Ar = Dep) without N2 fixation.
Reaction of amidinate with anhydrous CoCl2 and NiI2 produced (DippNC(H)NDipp)Co(μ-Cl)2Li(THF)2 (18) and (η1-DippNC(H)NDipp)NiI3Li(THF)2(OEt2)2 (22) respectively. Reduction of 18 and 22 furnished unprecedented low-coordinate complex [M(μ-η2-DippNC(H)NDipp)]2 (20: M = Co; 24: M = Ni). Moreover, treatment of 22 with 1.5 equivalent KC8 produced mixed-valence (μ-I)[Ni(μ-η2-DippNC(H)NDipp)]2 (23).
(1) MacKay, B. A.; Fryzuk, M. D. Chem. Rev. 2004, 104, 385-401.
(2) Holland, P. L. Acc. Chem. Res. 2008, 41, 905-914.
(3) Cummins, C. C.; Baxter, S. M.; Wolczanski, P. T. J. Am. Chem. Soc. 1988, 110, 8731-8733.
(4) Lapointe, R. E.; Wolczanski, P. T.; Mitchell, J. F. J. Am. Chem. Soc. 1986, 108, 6382-6384.
(5) Laplaza, C. E.; Cummins, C. C. Science 1995, 268, 861-863.
(6) Bourget-Merle, L.; Lappert, M. F.; Severn, J. R. Chem. Rev. 2002, 102, 3031-3065.
(7) Chai, J. F.; Zhu, H. P.; Stuckl, A. C.; Roesky, H. W.; Magull, J.; Bencini, A.; Caneschi, A.; Gatteschi, D. J. Am. Chem. Soc. 2005, 127, 9201-9206.
(8) Smith, J. M.; Sadique, A. R.; Cundari, T. R.; Rodgers, K. R.; Lukat-Rodgers, G.; Lachicotte, R. J.; Flaschenriem, C. J.; Vela, J.; Holland, P. L. J. Am. Chem. Soc. 2006, 128, 756-769.
(9) Knobloch, D. J.; Toomey, H. E.; Chirik, P. J. J. Am. Chem. Soc. 2008, 130, 4248-+.
(10) Curley, J. J.; Sceats, E. L.; Cummins, C. C. J. Am. Chem. Soc. 2006, 128, 14036-14037.
(11) Cotton, F. A. M., C. A.; Walton, R. A., 1993.
(12) Brosset, C. Nature (London) 1935, 135, 874.
(13) Cotton, F. A. L., S. J. J. Am. Chem. Soc. 1964, 86, 4497.
(14) Cotton, F. A.; Daniels, L. M.; Falvello, L. R.; Matonic, J. H.; Murillo, C. A. Inorg. Chim. Acta 1997, 256, 269-275.
(15) Cotton, F. A.; Feng, X. J.; Murillo, C. A. Inorg. Chim. Acta 1997, 256, 303-308.
(16) Cotton, F. A.; Daniels, L. M.; Feng, X. J.; Maloney, D. J.; Matonic, J. H.; Murillo, C. A. Inorg. Chim. Acta 1997, 256, 291-301.
(17) Cotton, F. A.; Daniels, L. M.; Maloney, D. J.; Murillo, C. A. Inorg. Chim. Acta 1996, 249, 9-11.
(18) Cotton, F. A.; Daniels, L. M.; Maloney, D. J.; Matonic, J. H.; Murillo, C. A. Inorg. Chim. Acta 1997, 256, 283-289.
(19) Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. J. Am. Chem. Soc. 1988, 110, 1144-1154.
(20) Manojlovicmuir, L.; Muir, K. W.; Davis, W. M.; Mirza, H. A.; Puddephatt, R. J. Inorg. Chem. 1992, 31, 904-909.
(21) Delaet, D. L.; Fanwick, P. E.; Kubiak, C. P. Organometallics 1986, 5, 1807-1811.
(22) Hsu, C. W.; Yu, J. S. K.; Yen, C. H.; Lee, G. H.; Wang, Y.; Tsai, Y. C. Angew. Chem. Int. Ed. 2008, 47, 9933-9936.
(23) Tsai, Y. C.; Wang, P. Y.; Lin, K. M.; Chen, S. A.; Chen, J. M. Chem. Commun. 2008, 205-207.
(24) Tsai, Y. C.; Wang, P. Y.; Chen, S. A.; Chen, J. M. J. Am. Chem. Soc. 2007, 129, 8066-8067.
(25) Dai, X. L.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799.
(26) Panda, A.; Stender, M.; Wright, R. J.; Olmstead, M. M.; Klavins, P.; Power, P. P. Inorg. Chem. 2002, 41, 3909-3916.
(27) Monillas, W. H.; Yap, G. P. A.; MacAdams, L. A.; Theopold, K. H. J. Am. Chem. Soc. 2007, 129, 8090-8091.
(28) Cossairt, B. M.; Cummins, C. C. Angew. Chem. Int. Ed. 2008, 47, 8863-8866.
(29) Barbaro, P.; Di Vaira, M.; Peruzzini, M.; Costantini, S. S.; Stoppioni, P. Angew. Chem. Int. Ed. 2008, 47, 4425-4427.
(30) Piro, N. A.; Cummins, C. C. Angew. Chem. Int. Ed. 2009, 48, 934-938.
(31) Lynam, J. M. Angew. Chem. Int. Ed. 2008, 47, 831-833.
(32) Weber, L. Chem. Rev. 1992, 92, 1839-1906.
(33) Piro, N. A.; Cummins, C. C. J. Am. Chem. Soc. 2008, 130, 9524-9535.
(34) Seidel, W. W.; Summerscales, O. T.; Patrick, B. O.; Fryzuk, M. D. Angew. Chem. Int. Ed. 2009, 48, 115-117.
(35) Scherer, O. J.; Swarowsky, M.; Wolmershauser, G. Organometallics 1989, 8, 841-842.
(36) Ghilardi, C. A.; Midollini, S.; Orlandini, A.; Sacconi, L. Inorg. Chem. 1980, 19, 301-306.
(37) Di Vaira, M.; Ehses, M. P.; Peruzzini, M.; Stoppioni, P. Polyhedron 1999, 18, 2331-2336.
(38) Yao, S.; Bill, E.; Milsmann, C.; Wieghardt, K.; Driess, M. Angew. Chem. Int. Ed. 2008, 47, 7110-7113.
(39) Yao, S. L.; Milsmann, C.; Bill, E.; Wieghardt, K.; Driess, M. J. Am. Chem. Soc. 2008, 130, 13536-+.
(40) Ghilardi, C. A.; Mealli, C.; Midollini, S.; Nefedov, V. I.; Orlandini, A.; Sacconi, L. Inorg. Chem. 1980, 19, 2454-2462.
(41) Tennyson, A. G.; Dhar, S.; Lippard, S. J. J. Am. Chem. Soc. 2008, 130, 15087-15098.
(42) Lei, H.; Ellis, B. D.; Ni, C. B.; Grandjean, F.; Long, G. J.; Power, P. P. Inorg. Chem. 2008, 47, 10205-10207.
(43) Maroney, M. J.; Trogler, W. C. J. Am. Chem. Soc. 1984, 106, 4144-4151.
(44) Pool, J. A.; Bernskoetter, W. H.; Chirik, P. J. J. Am. Chem. Soc. 2004, 126, 14326-14327.
(45) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911-2924.
(46) Ozerov, O. V.; Patrick, B. O.; Ladipo, F. T. J. Am. Chem. Soc. 2000, 122, 6423-6431.
(47) Bockmeulen, H. A.; Holloway, R. G.; Parkins, A. W.; Penfold, B. R. J. Chem. Soc.-Chem. Commun. 1976, 298-299.
(48) Nguyen, T.; Merrill, W. A.; Ni, C.; Lei, H.; Fettinger, J. C.; Ellis, B. D.; Long, G. L.; Brynda, M.; Power, P. P. Angew. Chem. Int. Ed. 2008, 47, 9115-9117.
(49) Basuli, F.; Kilgore, U. J.; Brown, D.; Huffman, J. C.; Mindiola, D. J. Organometallics 2004, 23, 6166-6175.
(50) Nijhuis, C. A.; Jellema, E.; Sciarone, T. J. J.; Meetsma, A.; Budzelaar, P. H. M.; Hessen, B. Eur. J. Inorg. Chem. 2005, 2089-2099.
(51) Amisial, L. D.; Dai, X. L.; Kinney, R. A.; Krishnaswamy, A.; Warren, T. H. Inorg. Chem. 2004, 43, 6537-6539.
(52) Yliheikkila, K.; Axenov, K.; Raisanen, M. T.; Klinga, M.; Lankinen, M. P.; Kettunen, M.; Leskela, M.; Repo, T. Organometallics 2007, 26, 980-987.
(53) Hocher, T.; Salisbury, B. A.; Theopold, K. H.; Hey-Hawkins, E. Polyhedron 2004, 23, 1393-1399.
(54) Fryzuk, M. D.; Love, J. B.; Rettig, S. J.; Young, V. G. Science 1997, 275, 1445-1447.
(55) Manzer, L. E. Inorg. Syn. 1982, 21, 135-140.
(56) Stender, M. W., R. J. Eichler, B. E.; Prust, J.; Olmstead, M. M.; Roesky, H. W.; Power, P. P. J. Chem. Soc., Dalton Trans. 2001, 3465-3469.
(57) Cheng, M. M., D. R.; Reczek, J. J.; Chamberlain, B. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 8738-8749.
(58) Podall, H. F., W. E.; Giraitis, A. P. J. Org. Chem. 1958, 23, 82-85.
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