第一部分我們利用高立體阻礙的二牙團硼代雙氮基脒配基PhB(N-2,6-iPr2C6
H3)2合成出的具有一個易解離甲苯分子的雙鉬金屬錯合物(η2：η2-C7H8)Mo2[µ-κ2-
PhB(N-2,6-iPr2C6H3)2]2 (3)，其3的甲苯分子在溶液中可進行解離，產生錯合物2；用其做為配基與鈷錯合物以及白磷進行反應。錯合物3與1當量的二羰基環戊二烯基鈷反應，藉由二羰基環戊二基鈷先解離出一個羰基得到錯合物[µ-κ2-OCCo(Cp)]Mo2[µ-κ2-PhB(N-2,6-iPr2C6H3)2]2 (4)。錯合物3與1當量的白磷反應，再以3.5當量鉀石墨還原後加入2當量冠醚後，得到錯合物[K (2.2.2-cryptand)]( µ-η1-P){Mo[μ-κ2-PhB(N-2,6-iPr2C6H3)2]2}2 (6a)和錯合物[K(18-C-
6)]3 (η3-P3)(η2-P2){Mo[μ-κ2-PhB(N-2,6-iPr2C6H3)2]2}2 (6b)
第二部分我們曾利用矽化雙胺基配基成功得到雙鉬四重鍵錯合物，以不同矽化雙胺基配基製備雙鉬四重鍵錯合物進行研究探討。配基Li2[Ph2Si(N-2,6-iPr2C6H3)2](Et2O)2 (L1)、Li2[Ph(CH3)Si(N-2,6-iPr2C6H3)2](Et2O)2 (L2)無法與金屬配位且更進一步合成出雙鉬金屬四重鍵；改變雙氮輔基的大小Li2[Ph2Si(N-2,6-Et2C6H3)2](Et2O)2 (L7)、Li2[Ph(CH3)Si(N-2,6-Et2C6H3)2](Et2O)2 (L8)、Li2[(CH3)2Si(N-2,6-Et2C6H3)2] (Et2O)2 (L10)、Li2[iPr2Si(N-2,6-Et2C6H3)2](Et2O)2 (L11)
，只有配基L7、L8成功得到錯合物(η1-H)Mo2[µ-κ2-Ph2Si(N-2,6-Et2C6H3)(N-2-Et-6-
(κ1-CH)CH3-C6H3)][µ-κ2-Ph2Si(N-2,6-Et2C6H3)2] (9)以及錯合物(η1-H)Mo2[µ-κ2-Ph
(CH3)Si(N-2,6-Et2C6H3)(N-2-Et-6-(κ1-CH)CH3-C6H3)][µ-κ2-Ph(CH3)Si(N-2,6-Et2C6H3)2] (11)；錯合物9與11皆發生分子內碳-氫活化，將其進一步與1當量苯乙炔反應得到錯合物 (η1-CCPh)Mo2[µ-κ2-Ph2Si(N-2,6-Et2C6H3)(N-2-Et-6-(κ1-CH)CH3-
C6H3)][µ-κ2-Ph2Si(N-2,6-Et2C6H3)2] (10)。從實驗結果觀察得到以矽原子上的烷基取代基是傾向於拉電子基團以利於與MoCl3(THF)3進行反應且進一步還原得到雙鉬四重鍵錯合物。

In the first part of this thesis, a boraamidinate ligand stabilized dimolybdenum quadruple bonded complex (η2：η2-C7H8)Mo2[µ-κ2-PhB(N-2,6-iPr2C6H3)2]2 (3) served as a ligand and stabilized a cobalt complex. Reaction of 3 with 1equiv. of CpCo(CO)2 gave [µ-κ2-OCCo(Cp)]Mo2[µ-κ2-PhB(N-2,6-iPr2C6H3)2]2 (4) by the loss of one carbonyl group. Moreover, white phosphorous activation has been done by the treatment of 3 with one equiv. of white phosphorus, the resultant species underwent three electron reduction in presence of crown ether and produced [K (2.2.2-cryptand)]( µ-η1-P){Mo[μ-κ2-PhB(N-2,6-iPr2C6H3)2]2}2 (6a) and [K(18-C-6)]3 (η3-P3)(η2-P2){Mo[μ-κ2-PhB(N-2,6-iPr2C6H3)2]2}2 (6b). Interestingly, complex 6a has bridge of P and complex 6b has two types of non cyclo-P3 and P2 units.
The second part shows, various silyldiamido ligands were successfully synthesized and tested for the synthesis of dimolybdenum quadruply bonded complexes. Ligands Li2[Ph2Si(N-2,6-iPr2C6H3)2](Et2O)2 (L1) and Li2[Ph(CH3)Si
(N-2,6-iPr2C6H3)2](Et2O)2 (L2) cannot give quadruply bonded dimolybdenum complexes, probably due to high steric bulk on the ancillary ligands. Less strically bulky ligands Li2[Ph2Si(N-2,6-Et2C6H3)2](Et2O)2 (L7),Li2[Ph(CH3)Si(N-2,6-Et2C6H3)2]
(Et2O)2 (L8),Li2[(CH3)2Si(N-2,6-Et2C6H3)2] (Et2O)2 (L10) and Li2[iPr2Si(N-2,6-Et2C6
H3)2](Et2O)2 (L11) were employed for the synthesis of dimolybdenum complexes but L7 and L8 were succeeded to give dimolybdenum complexes (η1-H)Mo2[µ-κ2-Ph2Si
(N-2,6-Et2C6H3)(N-2-Et-6-(κ1-CH)CH3-C6H3)][µ-κ2-Ph2Si(N-2,6-Et2C6H3)2] (9) and (η1-H)Mo2[µ-κ2-Ph(CH3)Si(N-2,6-Et2C6H3)(N-2-Et-6-(κ1-CH)CH3-C6H3)][µ-κ2-Ph(CH3)Si(N-2,6-Et2C6H3)2] (11). In both 9 and 11 intramolecular C-H bond activation was observed. Furthermore, reaction of 9 with one equivalent phenylacetylene gave (η1-CCPh)Mo2[µ-κ2-Ph2Si(N-2,6-Et2C6H3)(N-2-Et-6-(κ1-CH)CH3-C6H3)][µ-κ2-Ph2Si
(N-2,6-Et2C6H3)2](10).
Based on hese results, the electron withdrawing groups on silicon atom facilitate the isolation of dimolybdenum quadruple bonded complexes.

1. Cotton, F. A.; Curtis, M. F.; Harris, C. B.; Johnson, B. F. G.; Lippard, S. J.; Margue, J. T.;
Robinson, W. R.; Wood, J.W. Science 1964, 145, 1305.
2. Lawton, D.; Mason, R. J. Am. Chem. Soc. 1965, 87, 921.
3. Cotton, F. A.;Murillo, C. A.;Walton, R. A., Ed. Multiple Bonds Between Metal Atoms; 3rd
ed. Springer Science and Business Media, Inc.: New York, 2005.
4. Nguyen, T.; Sutton, A. D.; Brynda, S.; Fettinger, J. C.; Long, G. J.; Power, P. P. Science
2005, 310, 844.
5. Frenking, G. Science 2005, 310, 796.
6. Tsai, Y.-C.; Chen, H.-Z.; Chang, C.-C.; Yu, J.-S. K.; Lee, G.-H.; Wang, Y.; Kuo, T.-S. J.
Am. Chem. Soc. 2009, 131, 12534.
7. (a)Harisomayajula, N. V. S.; Nair, A. K.; Tsai, Y.-C. Chem. Commun. 2014, 50, 3391.
(b) Nair, A. K.; Harisomayajula, N. V. S.; Tsai, Y.-C. Inorganica Chimica Acta 2015,
424, 51.
8. (a)Chen, H.-Z.; Liu, S.-C.; Yen, C.-H.; Yu, J.-S. K.; Shieh, Y.-J.; Kuo. T.-S.; Tsai, Y.-C.
Angew. Chem. Int. Ed. 2012, 51, 10324. (b)Chen, H.-G.; Hsueh, H.-W.; Kuo, T.-S.; Tsai,
Y.-C. Angew. Chem. Int. Ed. 2013, 52, 10256. (c)Lu, D.-Y.; Chen, P. P.-Y.; Kuo, T.-S.;
Tsai, Y.-C. Angew. Chem. Int. Ed. 2015, 54, 9106.
9. (a)Chen, Y.; Sakaki, S. Dalton Transactions 2014, 43, 11478. (b)Karad, S. M.; Liu, R.-S.
Angew. Chem. Int. Ed. 2014, 53, 9027.
10. Woodward, R. B.; Hoffmann, R. J. Am. Chem. Soc. 1965, 87, 395.
11. Kobayashi, S. et al. Angew. Chem. Int. Ed. 2006, 45, 3816.
12. Clouston, L. J.; Siedschlag, R. B.; Rudd, P. A.; Plans, N.; Hu, S.; Miller, A. D.; Gagliardi,
L.; Lu, C. C. J. Am. Chem. Soc. 2013, 135, 13142.
13. Chivers, T.; Fedorchuk, C.; Parvez, M. Inorg. Chem. 2004, 43, 2643.
14. Lu, D.-Y.; Kuo, T.-S.; Tsai, Y.-C. Angew. Chem. Int. Ed. 2016, 55, 11614.
15. Hill, M. S.; Hitchcock, P. B. Organometallics. 2002, 21, 3258.
16. Tsai, Y.-C.; Lin, Y.-M.; Yu, J.-S. K.; Hwang, J.-K. J. Am. Chem. Soc. 2006, 128, 13980.
17. 林揚閔 國立清華大學化學研究所碩士論文 2006.
18. 周琬芳 國立清華大學化學研究所碩士論文 2016.
19. Pauling, L.; Simonetta, M. Journal of Chemical Physics 1952, 20, 29.
20. Kobayashi, N.;Kobayashi, Y.; Jpn. J. Appl. Phys. 1991, 30, L1699.
21. M. J. S. Dewar, Bull. Soc. Chim. Fr. 1951, C71.
102
22. J. Chatt, L. A. Duncanson, J. Chem. Soc. 1953, 2939.
23. (a)Staeb, T. H.; Chávez, J.;Gleiter, R.; Nuber, B. Eur. J. Inorg. Chem. 2005, 4090. (b)
Friedrich, W. G.; Jürgen, J. Organometallics. 2005, 24, 4613.
24. 簡彥庭 國立清華大學化學研究所碩士論文 2016.
25. Huber, K. P.;Herzberg, G. Constants of Diatomic Molecules, vol. IV of Molecular
Spectra and Molecular Structure 1979.
26. Pettersson, L. G. M.; Persson, B. J. Chem. Phys. 1993, 170, 149.
27. Scherer, O. J.; Winter, R.; Wolmersha¨user, G. Z. Anorg. Allg. Chem. 1993, 619,
827.
28. Chirik, P. J.; Pool, J. A.; Lobkovsky, E. Angew. Chem., Int. Ed. 2002, 41, 3463.
29. Seidel, W. W.; Summerscales, O. T.; Patrick, B. O.; Fryzuk, M. D. Angew. Chem.,
Int. Ed. 2009, 48, 115.
30. Stephens, F. H. Ph.D. thesis, Massachusetts Institute of Technology, 2004.
31. Velian, A.; Cummins, C. C. Chem. Sci. 2012, 3, 1003.
32. Scherer, O. J.; Werner, B.; Heckmann, G.; Wolmershauser, G. Angew. Chem.,
Int. Ed. Engl. 1991, 30, 553.
33. (a) Cotton, F. A.; Murillo, L. A.; Walton, R. A. Multiple Bonds Between Metal
Atoms, 3rd ed., Springer, Berlin, 2005.(b) Group 6 Metal–Metal Bonds:
Chisholm, M. H; Patmore, N. J. in Molecular Metal–Metal Bonds (Ed.: S. T.
Liddle), Wiley-VCH, Weinheim, 2015, 139.
34. Corbridge, D. E. C.; Lowe, E. J. Nature 1952, 4328, 629.
35. Scherer, O. J.; Sitzmann, H.; Wolmersha¨user, G.Z. J. Organomet. Chem. 1984,
268, C9
36. Goh, L. Y.; Chu, C. K.; Wong, R. C. S.; Hambley, T. W. J. Chem. Soc., Dalton
Trans. 1989, 1951–1956.
37. Di Vaira, M.; Ghilardi, C. A.; Midollini, S.; Sacconi, L. J. Am. Chem. Soc. 1978,
100, 2550.
38. 莊馥戎 國立清華大學化學研究所碩士論文 2014.
39. 顏君旭 國立清華大學化學研究所碩士論文 2009.
40. (a)Kempe, R.; Noor, A.; Glatz, G.; Müller, R.; Kaupp, M.; Demeshko, S. Z. Anorg. Allg.
Chem. 2009, 635, 1149. (b)Kempe, R.; Noor, A.; Bauer, T.; Todorova, T. K.; Weber, B.
Chem. Eur. J. 2013, 19, 9825.
41. Stoffelbach, F.; Saurenz, D.; Poli, R. Eur.J. Inorg. Chem. 2001, 21, 2699.
42. Naturforsch, Z. Teil. B: Chem. Sci. 2000, 55 , 352.
43. Murugavel, R.; Palanisami, N. Journal of Organometallic Chemistry 2006, 691 , 3260.
44. 陳宏章 國立清華大學化學研究所碩士論文 2011.
45. Eliel, E. L.;Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds. Wiley,
New York
103
46. Eliel, E. L.; Allinger, N. L.; Angyal, S. J.; Morrison, G. A. Conformational Analysis.
New York, 1965.
47. Hirsch, J.A. Topics in Stereochemistry. New York: John Wiley & Sons,Inc. 1967, 199.
48. Romers, C.; Altona, C.; Buys, H. R.; Havinga, E. Topics in Stereochemistry . New York:
John Wiley & Sons,Inc. 1969, 40.
49. Ryan, T. R.; McCinnis, R. N.; McCarley, R. E. J. Am. Chem. Soc. 1978, 100, 7900.
50. Chisholm, M. H.;Macintosh, A. M. Chem. Rev. 2005, 105, 2949.