臺灣博碩士論文加值系統

本論文共分為三章，第一章探討含多芽磷配位基與金屬四重鍵化合物的合成、光譜與結構。第二章探討含多芽氮配位基及其陰離子與雙鉬化合物之合成、光譜與結構。第三章探討由碳酸根離子結合的環狀六核四重鍵化合物的合成、光譜與結構。第一章：Mo2(O2CCR3)2X2(PPh3)2 與etp在CH2X2中反應可製備含橋接醋酸基及多芽磷配位基的四重鍵化合物Mo2(O2CCR3)X3(h3-etp) (R = H，X = Br，1；R = F，X = Cl，2；R = F，X = Br，3；etp = Ph2PCH2CH2P(Ph) CH2CH2PPh2)。其中1的結構可由單晶X-ray解析決定，此類化合物的dRd* 電子轉移的能量，31P{1H}-NMR的位移與31P{1H}-31P{1H} 的偶合常數均與鹵素及醋酸根的特性有關，經Mo-Mo四重鍵的偶合常數JP-Mo-Mo-P為20 ± 2 Hz。由Mo2(O2CPrn)4、PPh3與(CH3)3SiX(X = Cl，Br)在THF中反應可合成Mo2(O2CPrn)2X2(PPh3)2(X = Cl，4；X = Br，5)。利用Mo2(O2CPrn)2X2(PPh3)2與etp反應可製備含橋接丁酸基及多芽磷配位基的四重鍵化合物Mo2(O2CPrn)X3(h3-etp)(X = Cl，6；X = Br，7)，其中化合物4與5的結構由單晶X-ray解析決定。由化合物6及7的UV-vis與NMR光譜比較可知，烷基的鏈長增長並不影響δ →δ*吸收之能量與NMR的位移及偶合常數。第二章： trans-Mo2(O2CCR3)2X2(PPh3)2與一當量的Hdpa (Hdpa = bis (2-pyridyl)amine)在CH2Cl2中反應形成Mo2 (O2CCR3)2 X2(h2-Hdpa)(R = H，X = Cl, 8；R = H，X = Br, 9；R= F，X = Cl, 10；R = F，X = Br, 11)。將Hdpa 及Mo2(O2CCF3)2Br2(PPh3)2分別溶於ether及CH2Cl2中，利用合成養晶法可以得到Mo2(η2-dpa)4，12，及Mo2(O2CCF3)4(η1-HO2CCF3)2．2 Hdpa，13。 Mo2(O2CCF3)2Cl2(PPh3)2與四當量的HDpyF配位基( HDpyF = Bis(2-pyridyl)formamidine)在CH2Cl2中反應形成Mo2(η2-DpyF)4，14，此化合物亦可利用Mo2(O2CCH3)4及DpyF-在THF中反應形成。在化合物14的結構中DpyF-配位基的中央兩個氮原子橋接於金屬中心而端點兩個氮原子則未鍵結。由Cr(CO)6與1當量的HDpyF在THF中反應形成Cr(CO)4(η2-HDpyF)，15，化合物15的HDpyF配位基的雙配位的形式配位於金屬中心。化合物Mo2(O2CCH3)2X2(PPh3)2與二當量的bpma(bpma= 2, 2''-dipicolylamine)在THF中反應形成[Mo2O2(μ-O)2(bpma)2][X2] (X = Cl，16；Br，17)。利用Mo2(O2CCF3)2(CH3CN)6(BF4)2與二當量的bpma在CH3CN中反應可得到[Mo2O2(μ-O)2(bpma)2][BF4] 2，18，利用液體擴散法，將[Mo2O2(μ-O)2(bpma)2][BF4]2溶於CH2Cl2中，再以ether做液體擴散，可以得 [Mo2O2(μ-O)2(bpma)2][Cl][BF4]，19。由Mo2 (O2CCF3)4與二當量的H2tpa( H2tpa= Tripyridyldiamine)在THF中反應形成Mo2O2(μ-O)2(H2tpa)2(CF3COO)2，20。這些化合物的結構均可以單晶X-ray解析決定，這些化合物均含橋接之氧原子，而Mo-Mo間的距離屬於單鍵的範圍。第三章：[trans-Mo2(O2CCF3)2(CH3CN)6][BF4]2與K2CO3 及dppa (dppa = N,N-Bis(diphenylphosphino)amine)在CH2Cl2中反應可形成{[trans-Mo2(O2CCF3)2(m-dppa)]3(μ6-CO3)(μ2-Cl)3}F，21。[trans-Mo2(O2CCF3)2(CH3CN)6][BF4]2與K2CO3 及dppa在CH3CN中反應，隨後加入ZnX2( X = Br或I )可得到{[trans-Mo2(O2CCF3)2(m-dppa)]3(μ6-CO3)(μ2-X)3}F( X = Br，22；X = I，23 )，在這三個化合物中， CO32-鍵結三個四重鍵雙核化合物，且軸向位置由鹵素原子鍵結。這些化合物是第一個具平面形式的六核鉬化合物。 若利用[Mo2(O2CCF3)2(CH3CN)6][BF4]2 與dppa 在CH3CN 中反應而不加入K2CO3則可得[Mo2(O2CCF3)2 (dppa)2][BF4]2 ， 24 。

This thesis includes three chapters. The first chapter discusses syntheses, spectra and structures of quadruply bonded complexescontaining bridging h3-etp ligands (etp =Ph2PCH2CH2P(Ph)CH2CH2 PCH2PPh2). The second chapter discusses syntheses, spectra and stuctures of quadruply bonded complexes containing polydentate nitrogeneous ligands. The third chapter discusses novel cyclic hexanuclear complexes containing quadruply bonded units joined by m6-carbonate ions.The quadruply bonded complexes containing bridging acetate and polydentate phosphine ligands of the type Mo2(O2CCR3)X3(η3-etp) (R = H, X = Br, 1; R = F, X = Cl, 2; R = F, X = Br, 3; ) were prepared by reactions of Mo2(O2CCR3)2X2(PPh3)2 with etp in CH2X2 (X = Cl or Br). Their UV-vis and 31P{1H}-NMR spectra have been recorded and the structure of 1 has been determined by X-ray crystallography. The δ →δ* transition energy, 31P{1H}-NMR chemical shift and coupling constant were found to be dependent on the nature of the halogen atom . The though metal-metal quadruple bond coupling constant ︲3JP-Mo-Mo-P ︲ was determined to be 20 ± 2 Hz. The reaction of Mo2(O2CPrn)4 (X = Cl, 4; Br, 5) with PPh3 in THF, followed by addition of (CH3)3SiX (X = Cl, Br), afforded the complex Mo2(O2CPrn)2X2(PPh3)2. The quadruply bonded complexes containing bridging butyl acetate and polydentate phosphine ligand of the type Mo2(O2CPrn)X3(η3-etp)(X = Cl, 6; Br, 7) were prepared by reaction ofMo2(O2CPrn)2X2(PPh3)2 with etp. Their UV-vis and 31P{1H}-NMR spectra have been recorded and the structure of 4 and 5 have been determined by X-ray crystallography. The elongation of the alkyl group was found to have no effect on the δ→δ* energy, and 31P{1H}-NMR chemical shift. The reaction of trans-Mo2(O2CCR3)2X2(PPh3)2 with one equivalent of Hdpa (Hdpa = bis(2-pyridyl)amine) in CH2Cl2 afforded the complex cis-Mo2(O2CCR3)2X2(η2-Hdpa) (R = H, X = Cl, 8; R = H, X = Br, 9; R = F, X = Cl, 10, R = F, X = Br, 11). Layering of a Mo2(O2CCF3)4 solution in CH2Cl2 with Hdpa in ether produced red and yellow crystals, which were characterized to be Mo2(η2-dpa)4, 12, and Mo2(O2CCF3)4(η1-HO2CCF3)2 ． 2 Hdpa, 13, respectively. Complex 12 can also be prepared by reaction of trans-Mo2(O2CCR3)2X2(PPh3)2 with excess Hdpa. Their UV-vis and IR spectra have been recorded and the structures of 11,12 and 13 have been determined. The Hdpa ligand in 11 is coordinated to the metal centers through two terminal pyridine nitrogen atoms with a cis-N conformation. The dpa- ligands in 12 are bridged to the metal centers through one terminal nitrogen atom and the central nitrogen atom. The aligned-N conformation of the dpa- ligand is stabilized by both the intramolecular Mo---N and C-H---N interactions. In 13, the CF3COOH ligands coordinate to the metal centers in the axial positions with η1- bonding modes and the Hdpa molecules adapt cis-N conformations. The reaction of Mo2(O2CCF3)2Cl2(PPh3)2 with four equivalent of HDpyF (HDpyF = Bis(2-pyridyl)formamidine) in CH2Cl2 afforded the complex Mo2 (η2-DpyF)4 , 14. Complex 14 can also be prepared by reaction of Mo2(O2CCH3)4 with DpyF- in THF. Its UV-vis and IR spectra have been recorded and its structure of has been determined. The DpyF- ligand in 14 show two types of conformation ,i.e. cis and trans. Noticibly, while the cis conformation is stabilized by two intramolecular C-H---N interaction, the trans conformation is stabilized by one C-H---N and one Mo---N interactions. The reaction of Cr(CO)6 with one equivalent of HDpyF in THF afforded the complex Cr(CO)4(HDpyF), 15. The HDpyF ligand in 15 is chelated to the metal centers in a bidentate fashion.The reaction of Mo2(O2CCH3)2X2(PPh3)2 with two equivalents of bpma (bpma = 2, 2''-dipicolylamine) in THF afforded the complex [Mo2O2(μ-O)2(bpma)2][X]2(X = Cl, 16; Br, 17). The reaction of [Mo2(O2CCF3)2 (CH3CN)6][BF4]2 , 18 ,with two equivalents bpma in CH3CN afforded the complex [Mo2O2(μ-O)2(bpma)2][BF4]2. Layering of a [Mo2O2(μ-O)2(bpma)2][BF4]2 solution in CH2Cl2 with ether produced orange crystals, which were characterized to be [Mo2O2(μ-O)2(bpma)2][BF4][Cl], 19, Their UV-vis and IR spectra have been recorded and the structure of 16, 18, 19 have been determined by X-ray crystallography. The reaction of Mo2(O2CCF3)4with two equivalent H2tpda (H2tpda =Tripyridyldiamine) in THF afforded the complex (μ[Mo2O2-O)2(H2tpda)2][CF3COO]2, 20. All the structures of 16-20 contain bridging oxygen atoms and their Mo-Mo distances fall into the range for a Mo-Mo single bond. The reaction of [trans-Mo2(O2CCF3)2(CH3CN)6][BF4]2 with K2CO3 and dppa (dppa = N,N- Bis(diphenylphosphino)amine) in CH2Cl2 afforded the complex {[trans-Mo2(O2CCF3)2(μ-dppa)]3(m6-CO3)(m2-Cl)3}F, 21. Reaction of [trans-Mo2(O2CCF3)2(CH3CN)6][BF4]2 with K2CO3 and dppa in CH3CN, followed by addition of ZnX2 (X = Br or I) gave complexes of the type {[trans-Mo2(O2CCF3)2(μ-dppa)]3(μ6-CO3)(μ2-X)3}F (X = Br, 22; X = I, 23). The three quadruply bonded units in 21 - 23 are joined by CO32- ions and axially bridged by halide atoms. Each of the quadruply bonded units is bridged by a dppa ligand and two CF3COO- ligands which are trans to each other. Their UV-vis, IR and 31P{1H}NMR spectra have been recorded and their structures have been determined. They are the first cyclic, hexanuclear complexes containing quadruply bonded units joined by carbonate ions. The reaction of [trans-Mo2(O2CCF3)2(CH3CN)6][BF4]2 with and dppa in CH3CN, without addition of K2CO3, afforded the complex [trans-Mo2(O2CCF3)2 (dppa)2][BF4]2, 24.

封面
中文摘要
英文摘要
謝誌
目錄
表目錄
圖目錄
第一章 含多芽磷配位基與金屬四重鍵化合物的合成、光譜與結構研究
總反應圖
前言
實驗部份
X-ray 晶體結構解析
結果與討論
結論
第二章 含多芽氮配位基及其陰離子的雙鉬化合物合成、光譜與結構研究
總反應圖
前言
實驗部份
X-ray 晶體結構解析
結果與討論
結論
第三章 由碳酸根離子結合的環狀六核四重鍵化合物的合成、光譜與結構研究
總反應圖
前言
實驗部份
X-ray 晶體結構解析
結果與討論
結論
參考文獻
附錄

第一章 含多芽磷配位基與金屬四重鍵化合物的合成、光譜與結構研究(1) King, R.B.; Kapoor, P.N.; Kapoor, R.N. Inorg. Chem. 1971, 10,1841.(2) Guimerans, R.R.; Olmstead, M.M.; Balch, A.L. J.Am. Chem. Soc. 1983, 105, 1677(3)Cotton F. A.; Walton, R.A.; Multiple Bonds between MetalAtoms, 2nd ed.; Oxford University Press: London, 1993(4) Potenza, J. A.; Johnson, R. J.; Filippo, J. S. Inorg. Chem. 1976, 15, 2215.(5) Filippo, J. S.; Sniadoch, R. J. Inorg. Chem. 1976, 15, 2209.(6) Prout, K.; parkin, G.; Fail, J. J. Soc. Dalton Trans.1982, 2519(7) Arenivar, J. D.; Mainz, V. V.; Andersen R. A.; Zalkin, A. Inorg. Chem. 1982, 21, 2649.(8) Cotton, F. A.; Powell, G. L. Polyhedron, 1985, 4, 1669(9) Bakir, M.; Walton, R. A. Polyhedron, 1988, 7, 1279(10) Bates, P. A.; Nielson, A. Z.; Waters, J. M. Polyhedron,1987, 6, 2111.(11) Chen, J.-D.; Cotton, F. A. Inorg. Chem. 1991, 30, 6.(12) Cotton, F. A.; Hong, B. Inorg. Chem. 1993, 32, 2354.(13) Lee, C.-T.; Chiang, S.-F.; Chen, C.-T.; Chen J.-D.; Hsiao,C.-D. Inorg. Chem. 1996, 35, 2930.(14) Cotton, F. A.; Norman, J. G., J. Coord. Chem, 1971,1, 161.(15) Molecular Structure Corporation, MSC/AFC Diffracto meter Control Software, 1988, MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, U.S.A..(16) Molecular Structure Corporation, TEXSAN, TEXRAY Structure Analysis Package, 1993, MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, U.S.A.(17) Cotton, F. A.; Ilsley, W. H.; Kaim, W. Inorg. Chem. 1981, 20, 930.(18) Cotton, F. A.; Ilsley, W. H. 1981, 20, 572.(19) Hopkins, M. D.; Schaefer, W. P.; Bronikowski, M. J.;Woodruff, V. M. ; Miskowski, V. M.; Dallinger R. F.;Gray, H. B. J. Am. Chem. Soc. 1987, 109, 408.(20) Chen, J.-D.; Cotton F. A.; DeCaino, E. C. Inorg. Chim. Acta 1990, 176, 215.(21) Hopkins, M. D.; Gray H. B.; Miskowski, V. M. Poly- hedron, 1987,6 705.(22) Grim, S. O.; Barth, R. C. Mitchell J. D. ;Gaudio, J. D.Inorg. Chem., 1977, 16, 1776
第二章 含多芽氮配位基及其陰離子的雙鉬化合物合成、光譜與結構研究(1) Wu, L.-P. ; Field, P. ; T. Morrissey, T. ; Murphy, C. ; P. Nagle, P. ; Hathaway, B. ; Simmons, C. ; Thornton, P. J. Chem. Soc. Dalton Trans. 1990, 3835.(2) Rodig, O. R.; Brueckner, T.; Hurlburt, B. K. ; Schlatzer, R. K. ; Venable T. L. ; Sinn, E. J. Chem. Soc. Dalton Trans. 1981, 196.(3) Freeman, H. C. ; Snow, M. R. Acta Crystallogr., 1965, 18, 843.(4) Hurley, T. J. ; Robinson, M. A. Inorg. Chem., 1968, 7, 33.(5) Johnson, J. E. ; Jacobson, R. A. Acta Cryst., 1973, B29, 1669.(6) Pyrka, G. J. ; El-Mekki, M. ; Pinkerton, A. A. J. Chem. Soc. Chem. Comm., 1991, 84.(7) (a) Yang, E.-C. ; Cheng, M.-C. ; Tsai ,M.-S.; Peng, S.-M. J. Chem. Soc.,Chem. Comm., 1994, 2377. (b) Cotton, F. A. ; Daniels, L. M. ; Jordan IV, G. T. J. Chem. Soc., Chem. Comm., 1997, 421. (c) Cotton, F. A.; Daniels, L. M. ; Jordan IV, G. T. ; Murillo, C. A. J. Am Chem. Soc. 1997, 119, 10377.(8) Sheu, J.-T. ; Lin, C.-C.; Chao, I. ; Wang, C.-C. ; Peng, S.-M. J. Chem. Soc.,Chem. Comm., 1996, 315.(9) Cotton, F. A. ; Daniels, L. M. ; Murillo, C. A.; Pascual, I.J. Am Chem. Soc., 1997, 119, 10223.(10) Edema, J. J. H. ; Gambarotta, S. ; Meetsma, A. ;Spek, A.S. ; Smeets, W.J.J. ; Chiang, M.Y. J.Chem.Soc.Dalton Trans.,1993, 789.(11)Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Wang, X. Chem. Commun.1998, 39.(12) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Wang, X. Inorg. Chem. Commun.1998, 1,281.(13) Glern, J.; Goodson, P. A.;Hodgson, D. J.; Michelsen, K.; Nielsen,K. M.; Weihe, H. Inorg. Chem. 1992, 31, 461.(14) Jenkins, H. A.; Yap, G. P. A.; Puddephatt,R. J. Organometallics,1997, 16, 1946.(15)Brignole, A. B.; Cotton, F. A. Inorg. Synth. 1972, 13, 81.(16)Bakir, M. ; Walton, R. A. Polyhedron, 1988, 7, 1279.(17)Suen, M.-C.; Chiang, S.-F. ; Chen, J.-D. ; Chern, S.-S. ; Hsiao, C.-D. J. Chin. Chem. Soc., 1998, 45, 263.(18)Shieh, S.-J.; Chou, C.-C.;Lee, G.-H.; Wang,C.-C.; Peng,S.-M. Chem. Commun.1997, 56.(19) SMART/SAINT/ASTRO, Release 4.03, Siemens Energy &Automation, Inc., Madison, Wisconsin, USA, 1995.(20) Sheldrick, G. M. ''SHELXTL PLUS, Release 4.1'',Siemens Analytical X-ray Instruments Inc., Karlsruche, Germany, 1991(21) Agaskar, P. ; Cotton, F. A. Inorg. Chim. Acta., 1984, 83,33.(22) Chen, J.-D. ; Cotton, F. A.; Kang, S.-J. Inorg. Chim.Acta, 1991 ,190 ,103.(23) Cotton, F. A. ; Fanwick, P. E. ; Niswander R. H. ;Sekutowski, J. C. J. Am Chem. Soc., 1978, 100, 4725.(24) Cotton, F. A. ; Niswander, R. H. ; Sekutowski, J. C. Inorg. Chem., 1978, 17, 3541.(25) Lawton, D.; mason, R. J. Am. Chem. Soc.,1965,87, 921.(26) Cotton, F. A. ; J. G. Norman, J. G. J. Am. Chem. Soc.,1972, 94, 5967.(27) Girolami, G. S. ; Andersen, R. A. Inorg. Chem., 1982,21, 1318.(28) Cotton, F.A. Advanced inorganic chemistry, 828.
第三章 由碳酸根離子結合的環狀六核四重鍵化合物的合成、光譜與結構研究(1) Cotton, F. A.; Walton, R. A. Multiple Bonds between Metal Atoms, 2nd ed; Oxford University Press: London, 1993.(2) Cayton, R. H.; Chisholm, M. H.; Huffman, J. C.; Lobkovsky, E. B. J. Am. Chem. Soc. 1991, 113, 8709.(3) (a) Ryan, T. R.; McCarley, R. E. Inorg. Chem. 1982, 21, 2072. (b)Cotton, F. A.; Powell, G. L. Inorg. Chem. 1983, 22, 871. (c)Cotton, F. A.; Shang, M. J. Cluster Sci. 1991, 2, 121. (d)Carlin, R. T.; McCarley, R. E. Inorg. Chem. 1989, 28, 3432. (e)Chen, J.-D.; Cotton, F. A.. J. Am. Chem. Soc. 1991, 113, 5857. (f) Cotton, F. A.; Hong, B.; Shang, M. Inorg. Chem. 1993, 32, 4876.(4) Cotton, F. A.; Daniels, L. M.; Jordan, G.T.; Lin, C.; Murillo, C. A.; J. Am. Chem. Soc. 1998, 120, 3398.(5) Mak, T. C. W.; Li, P.-J.; Zheng, C.-M.; Huang, K.-Y. J. Chem.Soc., Chem. Comm. 1986, 1597.(6) Deacon, G. B.; Feng, T.; Hockless, D. C. R.; Junk, P. C.; Skelton,B. W.; White, A. H. Chem. Comm. 1997, 342.(7) Dance, I. G.; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A.In Comprehensive Coordination Chemisty ,ed. 1987, 1, 135.(8) Acho, J. A.; Ren, T.; Yun, J. W.; Lippard, S. J. Inorg. Chem. 1995,34, 5226.(9) Lee, C.-T.; Chiang, S.-F.; Chen, C.-T.; Chen, J.-D.; Hsian, C.-D.Inorg. Chem. 1996, 35, 2930.(10) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Pascual, I. J. Am Chem. Soc. 1997, 119, 10223.(11) Einstein, F. W. B.; Willis, A. C. Inorg. Chem. 1981, 20, 609.(12) Harow, R. L.; Simonsen, S. H. Acta Crystallorg.,Sect. B. 1976,B32, 466.(13) Brotherton, P. D.; White, A. H. J. Chem. Soc.Dalton Trans. 1973,2338.(14) Healy, P. C.; White, A. H. J. Chem. Soc.Dalton Trans. 1972, 1913.(15) Cotton, F. A.; Felthouse, T. R. Inorg. Chem. 1980, 19, 320.(16) Ferguson, G.; Hawley, D. M. Acta Crystallorg.,Sect. B. 1974,B30, 103.(17) Kolks, G.; Lippard, S. J.; Wazczak, J. V. J. Am. Chem. Soc. 1980,102, 4832.(18) Susse, P. Acta Crystallorg.,1967, 22, 146.(19) Limberg, C.; Parsons, S.; Downs, A. J. J. Chem. Soc., Chem. Comm.1994, 497.(20) Day, E. F.; Huffman, J. C.; Folting, K.; Christou, G. J. Chem. Soc., Dalton Trans. 1997, 2837.(21) Wu, Y.-Y.; Chen, J.-D.; Liou, L.-S.; Wang, J.-C. Inorg. Chem. Acta.1997, 258 ,193.(22) Cotton, F. A.; Arnold, D. I.; Kuhn, F. E. Inorg. Chem. 1996, 35,4733.(23) Cotton, F. A.; Kuhn, F. E. Inorg. Chem. Acta. 1996, 152, 257.