臺灣博碩士論文加值系統

　　本論文主要是利用含氮多牙配子，三乙烯基四胺，N, N'-雙三胺丙基丁二胺等，及含磷雙牙團配子，1, 2-雙二苯膦乙烷和VIB族羰基金屬（鉬，鎢）在正癸烷或四氫喃溶劑中，合成含羰基零價金錯合物。並依據錯合物的紅外吸收光譜及元素分析等，作結構組成之鑑定。其中得到單晶的錯合物有(1)[Mo2(CO)8(trien)], (trien=H2N-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2); (2)[Mo2(CO)8(C10H26N4)], (C10H26N4=H2N-(CH2)3-NH-(CH2)4-NH-(CH2)3-NH2); (3) [Mo2(CO)9(C7H19N3)], (C7H19N3=H2N-CH2)3-NH-(CH2)4-NH2); (4) [fac-W(CO)3(η1-dppe(O))(η2-dppe)], (dppe=PPh2-(CH2); (4) [FAC-W(CO)3(η1-dppe(O))(η2-dppe)], (dppe=PPh2-(CH2)2-PPh2; (5) [fac-Mo(CO)3(η1-dppe)(η2-dppe)]等五種，以X-ray繞法完成其結構解析。
　　淡黃色的錯合物(1)晶體為單斜晶系(Monoclinic)，空間群為P21/c, a=14.102 (3),b=10.963 (2),c=14.517 (2)A, V=2038.8 (6)A3, β=114.70 (1) , Z=4, Rf=0.033, Rw=0.031結構為雙核雙鉗事五環形式。
　　黃色的錯合物(2)晶體為三斜晶系(Triclinic），空間群為P-1, a=8.478 (3), b=11.921 (2), c=13.920 (3)A, V=1239.8 (6)A3, α=92.91 (2),β=114.69 (2),γ=103.59 (2)Z=2, Rf=0.048, Rw=0.043.錯合物(2)是雙核雙鉗合六環形式。
　　黃色的錯合物(3)晶體為三斜晶系（Triclinic），空間群為P-1, a=8.006 (4), b=11.244(9), c=12.670 (3)A,V=1134.9 (1)A3,α=88.66 (4),β=85.76 (3),γ=87.20 (3)0,Z=2,Rf=0.046, Rw=0.048.錯合物(3)是一鉗合環一橋鍵的雙核結構。
　　黃色的錯合物(4)晶體為單斜晶系（Monoclinic），空間群為P21/c, a=9.776 (4),b=19.219 (6),c=26.032 (1)A, V=4859 (3)A3, β=96.56 (3)0, Z=4,Rf=0.034, Rw=0.031.錯合物(4)是一鉗合環及一懸吊式的單核結構。
　　淺黃色的錯合物(5)晶體為單斜晶系（Monoclinic），空間群為P21/a, a=9.797 (2),b=19.296 (3), c=26.015 (2)A, V=4871 (1)A3,β=96.92 (3)0, Z=4, Rf=0.088, Rw=0.094。錯合物(5)為三取代單核錯合物。

　　Metal carbonyl derivatives were synthesized by reactions of the VIB metal hexacarbonyls with polydentate nitrogen ligand, triethylenetetramine, N, N'-bis (3-aminopropyl) butane-1, 4-diamine, 1, 1, 4, 7, 7-pentamethyltriethylenetetramine and 1, 2-bis (diphenyl-phosphino) ethane (dppe) in refluxed n-decane or tetrahydrofuran (THF) and were identified by infrared spectra and elemental analysis. Among them, crystal structures of (1)[Mo2(CO)8(trien)], (trien=H2N-(CH2)2-NH-(CH2)2-NH-(CH2)2-NH2); (2)[Mo2(CO)8(C10H26N4)], (C10H26N4=H2N-(CH2)3-NH-(CH2)4-NH-(CH2)3-NH2); (3) [Mo2(CO)9(C7H19N3)], (C7H19N3=H2N-CH2)3-NH-(CH2)4-NH2); (4) [fac-W(CO)3(η1-dppe(O))(η2-dppe)], (dppe=PPh2-(CH2); (4) [FAC-W(CO)3(η1-dppe(O))(η2-dppe)], (dppe=PPh2-(CH2)2-PPh2; (5) [fac-Mo(CO)3(η1-dppe)(η2-dppe)] have been undertaken by X-ray diffraction method.
　　Light yellow crystals of (1) are monoclinic space group P21/c, a=14.102 (3), b=10.963 (2), c=14.517 (2)A, V=2038.8 (6), β=114.70 (1) Z=4.Final R values are Rf=0.033, Rw=0.031. The ligands (trien) were coordinated to metals to form two fivemembered chelating rings.
　　Yellow crystals of (2) are triclinic space group P-1 with , a=8.478 (3), b=11.921 (2), c=13.920 (3)A, V=1239.8 (6)A3, α=92.91 (2),β=114.69 (2),γ=103.59 (2)Z=2. Final R values are Rf=0.048, Rw=0.043. The dinuclear complex has two cis six- membered chelating rings.
　　Yellow crystals of (3) are triclinic space group P-1 with a=8.006 (4), b=11.244(9), c=12.670 (3)A,V=1134.9 (1)A3,α=88.66 (4),β=85.76 (3),γ=87.20 (3)Z=2. Final R values are Rf=0.046, Rw=0.048. The compound (3) has a chelating ring and single bridged structure.
　　Yellow crystals of (4) are monoclinic space group P21/c with a=9.776 (4),b=19.219 (6),c=26.032 (1)A, V=4859 (3)A3, β=96.56 (3)0,Z=4. Final R values are Rf=0.034, Rw=0.031. The compound (4) has a chelating ring and a dangled structure and is a trisubstituted mononuclear complex.
　　Light yellow crystals of (5) are monoclinic space group P21/a with a=9.797 (2),b=19.296 (3), c=26.015 (2)A, V=4871 (1)A3,β=96.92 (3)Z=4.Final R values are Rf=0.088, Rw=0.094.The compound (5) is a trisubstituted mononuclear complex.