In this thesis, the sterically hindered three-nitrogen donor ligand H2[N2Ndipp] (N2Ndipp = 4-methyl-2,6-(N-2,6-iPr2C6H3)2 pyridine) was chosen to synthesize low-coordinate multinuclear complexes. Treatment of Li2[N2Ndipp] with GeCl2．dioxane and SnCl2 respectively gives the dinuclear complexes M2[N2Ndipp]2 (1: M = Ge; 6: M = Sn). Upon reduction of 1 by KC8, a dinuclear germanium(I) complex K2Ge2[N2Ndipp]2 (2) is isolated and characterized, where the geometry of the Ge-Ge linkage adopts the first example of cis-bent conformation, and the Ge-Ge bond length is 2.5168(6) Å and recognized as a σ bond. After removing the K+ cation from 2 by 2 equiv of 18-crown-6 ether, the ionic compound [K(18-crown-6)]2Ge2[N2Ndipp]2 (3) was obtained, where the cis-bent geometry is maintained but the Ge-Ge bond length is slightly increased to 2.5371(11) Å by 0.02 Å. On the other hand, reduction of 6 with KC8 in the presence of 18-crown-6 ether only leads to the isolation of a mononuclear tin(II) complex [K(18-crown-6)]2{Sn[N2Ndipp]2} (7). Interestingly, reaction of 2 with GeCl2．dioxane results in the formation of a linear tetranuclear mixed-valence Ge(II)-Ge(I)-Ge(I)-Ge(II) complex (GeCl)2Ge2[N2Ndipp]2 (4), where the internal Ge(I)-Ge(I) bond length is significantly shortened to 2.4071(6) Å and the two external Ge(I)-Ge(II) bond lengths are 2.5169(7) and 2.5196(5) Å. Moreover, reaction of 2 with SnCl2 also produces a tetranuclear mixed-metal complex (SnCl)2Ge2[N2Ndipp]2 (5), which is isostructural with that of 4 and, surprisingly, the internal Ge(I)-Ge(I) bond length dramatically shrinks to 2.3735(6) Å and the two external Ge(I)-Sn(II) bonds length are 2.6807(6) and 2.6807(5) Å.
In addition, mixing the deportonated bulky amidinates Li(THF)2[C(R)(N-2,6-iPr2C6H3)2] (R = H, tBu) with AlCl3 gives rise to the formation of mononuclear aluminum complex, AlCl2[C(H)(N-2,6-iPr2C6H3)2] (8a) and AlCl2[C(tBu)(N-2,6-iPr2C6H3)2] (8b). However, attempts to isolate the dinuclear Al(I)-Al(I) bonded complexes upon reduction of 8a and 8b have been unsuccessful. All the said products are fully characterized by NMR spectroscopy and elemental analysis, and their molecular structures are determined by single crystal X-ray crystallography.

摘要................................................................................................................I
Abstract ....................................................................................................... III
目錄..............................................................................................................V
圖表目錄..................................................................................................VIII
第一章緒論.................................................................................................1
1.1前言.................................................................................................1
1.2主族元素的多重鍵.........................................................................1
1.3類過渡金屬的主族元素.................................................................4
1.4重主族元素的鍵結.........................................................................6
1.5主族分子與小分子的反應性....................................................... 11
1.5.1鍺與錫乙炔衍生物的還原........................................................17
1.6 14族重元素的反應性..................................................................19
1.6.1 二價鍺化合物的反應性...................................................22
第二章低價鍺雙金屬錯合物合成之結構探討.......................................24
2.1前言...............................................................................................24
2.2 錯合物Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (1)的合成與鑑定
.............................................................................................................28
2.3 錯合物K2Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (2)的合成與鑑
VI
定.........................................................................................................29
2.4 錯合物[K(18-crown-6)]2Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (3)
的合成與鑑定.....................................................................................35
2.5 錯合物[GeCl]2Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (4)的合成與
鑑定.....................................................................................................38
2.6 錯合物[SnCl]2Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (5)的合成與
鑑定.....................................................................................................43
其他嘗試.............................................................................................46
2.7 結果與討論..................................................................................50
第三章錫雙金屬錯合物及其他嘗試.......................................................56
3.1 前言..............................................................................................56
3.2錯合物Sn2[4-methyl-2,6-(NDipp)2pyridine]2 (6)的合成............58
3.3錯合物Sn[K(18-crown-6)]2 [4-methyl-2,6-(NDipp)2pyridine]2 (7)
的合成.................................................................................................61
3.4其他嘗試.......................................................................................63
3.4.1 化合物AlCl2[C(H)(N-2,6-iPr2-C6H3)2](Et2O) (8)的合成........63
第四章實驗步驟.......................................................................................66
1. 一般操作........................................................................................66
2. 實驗使用儀器................................................................................66
VII
3.實驗藥品與溶劑..............................................................................68
4. 使用藥品：....................................................................................68
5.實驗步驟..........................................................................................69
Li2[4-methylpyridine(2,6-NDipp)2](Et2O) 的合成
[ Li2[N2NDipp] ] ............................................................................69
Ge2[4-methyl-2,6-(NDipp)2pyridine]2 (1) 的合成
[ Ge2(N2NDipp)2 ] ..........................................................................70
(GeK)2[4-methyl-2,6-(NDipp)2pyridine]2 (2) 的合成
[ (GeK)2(N2NDipp)2 ].....................................................................70
Ge2[4-methyl-2,6-(NDipp)2pyridine]2[K(18-crown-6-ether)
(THF)]2 (3) 的合成.....................................................................72
(GeGeCl)2[4-methylpyridine(2,6-NDipp)2]2 (4) 的合成
[ (GeGeCl)2(N2NDipp)2 ] ...............................................................72
(GeSnCl)2[4-methylpyridine(2,6-NDipp)2]2 (5) 的合成
[ (GeSnCl)2[N2NDipp]2 ]................................................................74
Sn2[4-methyl-2,6-(NDipp)2pyridine]2 (6) 的合成
[ Sn2(N2NDipp)2 ] ..........................................................................75
Sn[4-methyl-2,6-(NDipp)2pyridine]2[K(18-crown-6-ether)
(THF)]2 (7) 的合成....................................................................76
AlCl2[C(H)(N-2,6-iPr2-C6H3)2] (Et2O) (8a) 的合成..................77
AlCl2[C(tBu)(N-2,6-iPr2-C6H3)2] (8b)的合成.............................78
VIII
Li2Ge5[4-methylpyridine(2,6-NDipp)2]4 (8c) 的合成 [Li2Ge5
[N2NDipp]4 ]...................................................................................79
附錄.............................................................................................................80
晶體資料.............................................................................................80
Reference:....................................................................................................88

(1) Dedieu, A.; Albright, T. A.; Hoffmann, R. J. Am. Chem. Soc. 1979, 101, 3141-3151.
(2) Klinkhammer, K. W. Angew. Chem. Int. Ed. 1997, 36, 2320-2322.
(3) Goldberg, D. E. J. Chem. Soc. Dalton Trans. 1986, 2387-2394.
(4) Jacobsen, H.; Ziegler, T. J. Am. Chem. Soc. 1994, 116, 3667-3679.
(5) Grev, R. S. Adv. Organomet. Chem. 1991, 33, 125-170.
(6) Carter, E. A.; Goddard, W. A. J. Phys. Chem. 1986, 90, 998-1001.
(7) Trinquier, G.; Malrieu, J. P. J. Am. Chem. Soc. 1987, 109, 5303-5315.
(8) Bleeke, J. R.; Xie, Y. F.; Peng, W. J.; Chiang, M. J. Am. Chem. Soc. 1989, 111, 4118-4120.
(9) Trinquier, G.; Malrieu, J. P.; Riviere, P. J. Am. Chem. Soc. 1982, 104, 4529-4533.
(10) Driess, M.; Grützmacher, H. Angew. Chem. Int. Ed. 1996, 35, 828-856.
(11) Power, P. P. Organometallics 2007, 26, 4362-4372.
(12) Power, P. P. Nature 2010, 463, 171-177.
(13) Roesky, H. W.; Kumar, S. S. Chem. Commun. 2005, 4027-4038.
(14) Mizuhata, Y.; Sasamori, T.; Tokitoh, N. Chem. Rev. 2009, 109, 3479-3511.
(15) Power, P. P. Chem. Rev. 1999, 99, 3463-3503.
(16) Gaspar, P. P.; West, R.; Macmillan Publishers Limited. All rights reserved: 1998, p 2463-2568.
(17) Stephan, D. W. Dalton Trans. 2009, 3129-3136.
(18) Power, P. P. Chem. Rev. 2003, 103, 739-809.
(19) Hicks, R. G. Org. Mol. Biochem 2007, 5, 1321-1338.
(20) Lee, V.; Ya; Nakamoto, M.; Sekiguchi, A. Chem. Lett. 2008, 37, 128-133.
(21) Breher, F. Coord. Chem. Rev. 2007, 215, 1007-1043.
(22) Dasent, W. E.; Macmillan Publishers Limited. All rights reserved: 1965.
(23) Taylor, M. J.; Macmillan Publishers Limited. All rights reserved: 1975.
(24) Pearson, R. G. J. Am. Chem. Soc. 1988, 110, 2092-2097.
(25) Davidson, P. J.; Lappert, M. F. Chem. Commun. 1973, 317.
(26) Goldberg, D. E.; Harris, D. H.; Lappert, M. F.; Thomas, K. M. Chem. Commun. 1976, 261-262.
(27) Wells, A. F.; Macmillan Publishers Limited. All rights reserved: 1986.
(28) Sturmann, M.; Weidenbruch, M.; Klinkhammer, K. W.; Lissner, F.; Marsmann, H. Organometallics 1998, 17, 4425-4428.
(29) West, R.; Fink, M. J.; Michl, J. Science 1981, 214, 1343-1344.
(30) Sekiguchi, A.; Kingo, R.; Ichinohe, M. Science 2004, 305, 1755-1757.
(31) Stender, M.; Phillips, A. D.; Wright, R. J.; Power, P. P. Angew. Chem. Int. Ed. 2002, 41, 1785-1787.
(32) Phillips, A. D.; Wright, R. J.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2002, 124, 5930-5931.
(33) Pu, L.; Twamley, B.; Power, P. P. J. Am. Chem. Soc. 2000, 122, 3524-3525.
(34) Spikes, G. H.; Fettinger, J. C.; Power, P. P. J. Am. Chem. Soc. 2005, 127, 12232-12233.
(35) Peng, Y. Chem. Commun. 2008, 6042-6044.
(36) Zhu, Z. Angew. Chem. Int. Ed. 2009, 48, 2031-2033.
(37) Chase, P. A.; Stephan, D. W. Angew. Chem. Int. Ed. 2008, 47, 7433-7437.
(38) Frey, G. D.; Lavallo, B.; Donnadieu, B.; Schoeller, W. W.; Bertrand, G. Science 2007, 316, 439-441.
(39) Zhao, J.; Goldman, A. S.; Hartwig, J. S. Science 2005, 307, 1080-1082.
(40) Peng, Y.; Ellis, B. D.; Wang, X.; Fettinger, J. C.; Power, P. P. Science 2009, 325, 1668-1670.
(41) Cui, C.; Brynda, M. A.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2004, 126, 6510-6511.
(42) Wang, X.; Peng, Y.; Olmstead, M. M.; Fettinger, J. C.; Power, P. P. J. Am. Chem. Soc. 2009, 131, 14164-14165.
(43) Dai, X.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799.
(44) Kühl, O. Coord. Chem. Rev. 2004, 248, 411-427.
(45) Driess, M.; Yao, S.; Brym, M.; van Wuellen, C. Angew. Chem., Int. Ed. 2006, 45, 4349-4352.
(46) Yao, S.; van Wuellen, C.; Driess, M. Chem. Commun. 2008, 5393-5395.
(47) Jana, A.; Nekoueishahraki, B.; Roesky, H. W.; Schulzke, C. Organometallics 2009, 28, 3763-3766.
(48) Jana, A.; Objartel, I.; Roesky, H. W.; Stalke, D. Inorg. Chem. 2009, 48, 7645-7649.
(49) Jana, A.; Objartel, I.; Roesky, H. W.; Stalke, D. Inorg. Chem. 2009, 48, 798-800.
(50) Jana, A.; Schulzke, C.; Roesky, H. W. J. Am. Chem. Soc. 2009, 131, 4600-4601.
(51) Yao, S.; Xiong, Y.; Driess, M. Chem. Commun. 2009, 6466-6468.
(52) Schafer, H.; Saak, W.; Weidenbruch, M. Organometallics 1999, 18, 3159-3163.
(53) Green, S. P.; Jones, C.; Junk, P. C.; Lippert, K.-A.; Stasch, A. Chem. Commun. 2006, 3978-3980.
(54) Kira, M.; Ishida, S.; Iwamoto, T.; Ichinohe, M.; Kabuto, C.; Ignatovich, L.; Sakurai, H. Chem. Lett. 1999, 28, 263-264.
(55) Leung, W.-P.; Chiu, W.-K.; Chong, K.-H.; Mak, T. C. W. Chem. Commun. 2009, 6822-6824.
(56) Wang, Y.; Robinson, G. H. Chem. Commun. 2009, 5201-5213.
(57) Weidenbruch, M. Organometallics 2003, 22, 4348-4360.
(58) Snow, J. T.; Murakami, S.; Masamune, S.; Williams, D. J. Tetrahedron Lett. 1984, 25, 4191-4194.
(59) Wang, W.; Yao, S.; van Wüllen, C.; Driess, M. J. Am. Chem. Soc. 2008, 130, 9640-9641.
(60) Wang, W.; Inoue, S.; Yao, S.; Driess, M. Chem. Commun. 2009, 2661-2663.
(61) Schafer, A.; Saak, W.; Weidenbruch, M. Organometallics 2002, 22, 215-217.
(62) Nagendran, S.; Sen, S. S.; Roesky, H. W.; Koley, D.; Grubmüller, H.; Pal, A.; Herbst-Irmer, R. Organometallics 2008, 27, 5459-5463.
(63) Rivard, E.; Power, P. P. Inorg. Chem. 2007, 46, 10047-10064.
(64) Pu, L.; Phillips, A. D.; Richards, A. F.; Stender, M.; Simons, R. S.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2003, 125, 11626-11636.
(65) Jambor, R.; Kascaronná, B.; Kirschner, Karl N.; Schürmann, M.; Jurkschat, K. Angew. Chem. Int. Ed. 2008, 47, 1650-1653.
(66) Lee, V. Y.; Fukawa, T.; Nakamoto, M.; Sekiguchi, A.; Tumanskii, B. L.; Karni, M.; Apeloig, Y. J. Am. Chem. Soc. 2006, 128, 11643-11651.
(67) Coles, M. P.; Swenson, D. C.; Jordan, R. F.; Young, V. G. Organometallics 1998, 17, 4042-4048.