雙螯合(binucleating)配位基1,1’-((1,8-Naphthyridine-2,7-diyl)-bis-(N-(2,6-diisopropylphenyl))methanimine) (NDI) (1)具有氧化還原活性，所以可使用於雙金屬錯合物的合成。以NDI為配位基可以製備雙鍺金屬錯合物 [Ge2Cl2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – (NDI)Ge2Cl2 (3)，還原後即可生成雙鍺烯錯合物[Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – (NDI)Ge2 (4)，其中配位基的氧化態會從0變成-1或-2。錯合物4可當配位基，分別與Ni(cod)2（cod: 1,5-Cyclooctadiene）和Ni(PPh3)4反應，可以得到具有七員環的雙鍺-鎳錯合物[Ni(η4-(1,4-cod))(κ2-(Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))))] – (NDI)Ge2Ni(cod) (6) 和 [Ni(PPh3)2(κ2-(Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))))] – (NDI)Ge2Ni(PPh3)2 (7)，中心金屬Ni(0)可以有效的活化小分子。
另外，化合物3與兩當量的三氯化硼(BCl3)反應，得到一種史無前例的三烯酮化合物[(BCl3)(B2Cl2)(μ3-κ1:κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – [(NDI)B2Cl2]BCl3 (8)。若將NDI配位基、鉀石墨和三氯化硼進行一鍋化反應，則會生成不同結構的雙硼錯合物[(BCl3)(BCl)(μ-κ1:κ2-(2,7-(CHN)2-C8H4N2)(N-2,6-iPr2C6H3)2)] – (NDI)B2Cl¬4 (9)。以上所有合成出來的產物，皆以經過核磁共振光譜、單晶X-ray繞射和元素分析鑑定。

A new binucleating redox-active ligand 1,1’-((1,8-Naphthyridine-2,7-diyl)-bis-(N-(2,6-diisopropylphenyl))methanimine) (NDI) (1) was prepared and utilized to stabilize dinuclear main group complexes. The oxidation state of NDI ligand changed from 0 to -1 or -2 when coordinating to germanium atoms in [Ge2Cl2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – (NDI)Ge2Cl2 (3) and its reduced product [Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – (NDI)Ge2 (4), respectively. The effect of oxidation state of ligand on reactivity of digermylene complexes was studied by comparing the differences in hydrogenation reaction of complexes 3 and 4. In addition, complex 4 was employed as a bidentate digermylene ligand to result in six-members ring nickel(0) substrates [Ni(η4-(1,4-cod))(κ2-(Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))))] – (NDI)Ge2Ni(cod) (6) and [Ni(PPh3)2(κ2-(Ge2(μ-κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))))] – (NDI)Ge2Ni(PPh3)2 (7), which aims to be used as an effective catalyst manipulating Ni(0) and Ge(II) supported by redox active ligand.
Furthermore, an unprecedented helicene species of triboron compound [(BCl3)(B2Cl2)(μ3-κ1:κ4-(2,7-((N-2,6-iPr2C6H3)CHN)2-C8H4N2))] – [(NDI)B2Cl2]BCl3 8 was achieved via transmetalation reaction when investigating reactivity of 3 with 2 equivalences of BCl3. On the other hand, one pot reaction of NDI, KC8 and BCl3, leading to the formation of another structurally different diboron molecule [(BCl3)(BCl)(μ-κ1:κ2-(2,7-(CHN)2-C8H4N2)(N-2,6-iPr2C6H3)2)] – (NDI)B2Cl¬4 (9), was also discussed. All complexes were characterised and confirmed by 1H, 13C NMR, X-ray crystallography and elemental analysis (EA).

List of Scheme V
List of Figure VI
List of Abbreviations VII
CHAPTER I: INTRODUCTION AND STUDY MOTIVATION 1
1. Redox-Active Supporting Ligand 1
2. N-heterocyclic divalent germanium complexes 7
3. Study motivation 15
CHAPTER II: RESULTS AND DISCUSSION 16
1. Synthesis of binucleating redox-active ligand based digermanium complexes 16
2. The influence of non-innocent ligand on reactivity of digermylene complexes 21
3. Synthesis of the Digermylene-supported Nickel(0) complex 23
4. Reactivity of Bis-(NDI)Ge2Cl2 with BCl3 26
5. Synthesis of the diboron complex (NDI)BClBCl3 9 29
CHAPTER III: EXPERIMENTAL SECTION 32
1. General information 32
2. Synthetic procedures 32
REFERENCES 39
APPENDIX 43
X-RAY CRYSTALLOGRAPHIC DATA 51

1. Grützmacher, H., Angew. Chem. Int. Ed., 2008, 47, 1814.
2. Kaim, W., Coord. Chem. Rev., 1987, 76, 187.
3. Lyaskovskyy, V.; de Bruin, B., ACS Catalysis, 2012, 2, 270.
4. Ringenberg, M. R.; Kokatam, S. L.; Heiden, Z. M.; Rauchfuss, T. B., J. Am. Chem. Soc., 2008, 130, 788.
5. Ringenberg, M. R.; Rauchfuss, T. B., Eur. J. Inorg. Chem., 2012, 2012, 490.
6. Muckerman, J. T.; Polyansky, D. E.; Wada, T.; Tanaka, K.; Fujita, E., Inorg. Chem., 2008, 47, 1787.
7. Boyer, J. L.; Rochford, J.; Tsai, M.-K.; Muckerman, J. T.; Fujita, E., Coord. Chem. Rev., 2010, 254, 309.
8. Bouwkamp, M. W.; Bowman, A. C.; Lobkovsky, E.; Chirik, P. J., J. Am. Chem. Soc., 2006, 128, 13340.
9. Chirik, P. J.; Wieghardt, K., Science, 2010, 327, 794.
10. Thompson, E. J.; Berben, L. A., Angew. Chem. Int. Ed., 2015, 54, 11642.
11. Veith, M.; Grosser, M., Zeitschrift für Naturforschung B, 1982, 37, 1375.
12. Arduengo III, A. J.; Harlow, R. L.; Kline, M., J. Am. Chem. Soc., 1991, 113, 361.
13. Meller, A.; Gräbe, C. P., Chemische Berichte, 1985, 118, 2020.
14. Herrmann, W. A.; Denk, M.; Behm, J.; Scherer, W.; Klingan, F. R.; Bock, H.; Solouki, B.; Wagner, M., Angew. Chem. Int. Ed., 1992, 31, 1485.
15. Trinquier, G.; Barthelat, J. C.; Satge, J., J. Am. Chem. Soc., 1982, 104, 5931.
16. Heinemann, C.; Herrmann, W. A.; Thiel, W., J. Organomet. Chem., 1994, 475, 73.
17. Pause, L.; Robert, M.; Heinicke, J.; Kühl, O., Perkin 2, 2001, 1383.
18. Lehmann, J. F.; Urquhart, S. G.; Ennis, L. E.; Hitchcock, A. P.; Hatano, K.; Gupta, S.; Denk, M. K., Organometallics, 1999, 18, 1862.
19. Kühl, O.; Lönnecke, P.; Heinicke, J., Polyhedron, 2001, 20, 2215.
20. Heinicke, J.; Oprea, A.; Kindermann, M. K.; Karpati, T.; Nyulászi, L.; Veszprémi, T., Chem. Eur. J., 1998, 4, 541.
21. Heinicke, J.; Oprea, A., Heteroat. Chem., 1998, 9, 439.
22. Pfeiffer, J.; Maringgele, W.; Noltemeyer, M.; Meller, A., Eur. J. Inorg. Chem., 1989, 122, 245.
23. Prokop, J.; Merica, R.; Glatz, F.; Veprek, S.; Klingan, F.; Herrmann, W., Organosilicon Chemistry Set: From Molecules to Materials, 1996, 815.
24. Vepřek, S.; Prokop, J.; Glatz, F.; Merica, R.; Klingan, F.; Herrmann, W., Chem. Mater., 1996, 8, 825.
25. Prokop, J.; Merica, R.; Glatz, F.; Veprek, S.; Klingan, F.-R.; Herrmann, W., J. Non-Cryst. Solids, 1996, 198, 1026.
26. Kobayashi, S.; Iwata, S.; Hiraishi, M., J. Am. Chem. Soc., 1994, 116, 6047.
27. Abakumov, G.; Cherkasov, V.; Piskunov, A.; Aivaz'yan, I.; Druzhkov, N. In New paramagnetic derivatives of N-heterocyclic germylenes: An EPR study, Doklady Chemistry, Springer: 2005; pp 189.
28. Akkari, A.; Byrne, J. J.; Saur, I.; Rima, G.; Gornitzka, H.; Barrau, J., J. Organomet. Chem., 2001, 622, 190.
29. Dias, H. R.; Wang, Z., J. Am. Chem. Soc., 1997, 119, 4650.
30. Vu, C.; Walker, D.; Wells, J.; Fox, S., J. Heterocycl. Chem, 2002, 39, 829.
31. Muresan, N.; Lu, C. C.; Ghosh, M.; Peters, J. C.; Abe, M.; Henling, L. M.; Weyhermöller, T.; Bill, E.; Wieghardt, K., Inorg. Chem., 2008, 47, 4579.
32. Vasudevan, K. V.; Vargas‐Baca, I.; Cowley, A. H., Angew. Chem. Int. Ed., 2009, 48, 8369.
33. Fedushkin, I. L.; Khvoinova, N. M.; Baurin, A. Y.; Fukin, G. K.; Cherkasov, V. K.; Bubnov, M. P., Inorg. Chem., 2004, 43, 7807.
34. Fedushkin, I. L.; Skatova, A. A.; Chudakova, V. A.; Khvoinova, N. M.; Baurin, A. Y.; Dechert, S.; Hummert, M.; Schumann, H., Organometallics, 2004, 23, 3714.
35. Li, J.; Schenk, C.; Goedecke, C.; Frenking, G.; Jones, C., J. Am. Chem. Soc., 2011, 133, 18622.
36. Spikes, G. H.; Fettinger, J. C.; Power, P. P., J. Am. Chem. Soc., 2005, 127, 12232.
37. Wang, Y.; Kostenko, A.; Yao, S.; Driess, M., J. Am. Chem. Soc., 2017, 139, 13499.
38. Lee, J.; Lee, C.; Lee, S. S.; Kang, S. O.; Ko, J., Chem. Commun, 2001, 1730.
39. Glockling, F.; McGregor, A.; Schneider, M.; Shearer, H., J. Inorg. Nucl. Chem., 1970, 32, 3101.
40. Gallego, D.; Brück, A.; Irran, E.; Meier, F.; Kaupp, M.; Driess, M.; Hartwig, J. F., J. Am. Chem. Soc., 2013, 135, 15617.
41. Fedushkin, I. L.; Markina, O. V.; Lukoyanov, A. N.; Morozov, A. G.; Baranov, E. V.; Maslov, M. O.; Ketkov, S. Y., Dalton Trans., 2013, 42, 7952.
42. Li, J.; Zhang, K.; Huang, H.; Yu, A.; Hu, H.; Cui, H.; Cui, C., Organometallics, 2013, 32, 1630.
43. Hinchliffe, A.; Mair, F. S.; McInnes, E. J.; Pritchard, R. G.; Warren, J. E., Dalton Trans., 2008, 222.
44. Hickox, H. P.; Wang, Y.; Luedecke, K. M.; Xie, Y.; Wei, P.; Carrillo, D.; Dominique, N. L.; Cui, D.; Schaefer, H. F.; Robinson, G. H., Dalton Trans., 2018, 47, 41.
45. Abram, U.; Lang, E. S.; Abram, S.; Wegmann, J.; Dilworth, J. R.; Kirmse, R.; Woollins, J. D., J. Chem. Soc., Dalton Trans., 1997, 623.
46. Baber, R. A.; Bull, A. E.; Charmant, J. P.; Norman, N. C.; Orpen, A. G., Acta Crystallographica Section E: Structure Reports Online, 2005, 61, 553.
47. Lee, J.; Lee, M. L.; Arnott, Z.; Jenkins, H. A.; Britten, J. F.; Vargas-Baca, I., New J. Chem., 2018.
48. Minkwitz, R.; Nass, R.; Preut, H., Zeitschrift für anorganische und allgemeine Chemie, 1987, 546, 99.
49. Clippard, P. H.; Hanson, J. C.; Taylor, R. C., J. Cryst. Mol. Struc., 1971, 1, 363.