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| 研究生： |
張凱傑 Chang, Kai-Chieh |
|---|---|
| 論文名稱： |
Synthesis and Reactivity of V2, Co2 and Ni2 Complexes 雙核釩、鈷、鎳錯合物的合成與化性研究 |
| 指導教授： |
蔡易州
Tsai, Yi-Chou |
| 口試委員: | |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2009 |
| 畢業學年度： | 97 |
| 語文別： | 中文 |
| 論文頁數： | 117 |
| 中文關鍵詞： | 雙核 、雙核鎳 、雙核鈷 、雙核釩 |
| 相關次數： | 點閱：4 下載：0 |
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將(Nacnac)DippCo(μ-Cl)2Li(THF)2 (Nacnac = HC(C(Me)NC6H3iPr2)2)在甲苯中利用KC8還原，可以成功的分離得到反三明治式雙核鈷錯合物－(μ-η2:η2-C7H8)[Co(Nacnac)Dipp]2 (1)，我們發現錯合物1對於小分子以及有機化合物皆有很好的反應性，產生許多新奇的鈷錯合物。利用1與白磷反應會得到以四個磷原子橋接的(μ-η4:η4-P4)[Co(Nacnac)Dipp]2 (2)，若再將2於100 ℃加熱四天，則會失去一個磷原子而產生(μ-η3:η3-P3)[Co(Nacnac)Dipp]2 (3)。另外利用1加入十六族元素後分別可分離得到[Co(Nacnac)Dipp(μ-X)]2 (4: X = S; 5: X = Se)與[Co(Nacnac)Dipp(μ-TeH)]2 (6)。而通入過量的一氧化氮則會得到逆磁性的Co(Nacnac)Dipp(NO)2 (7)。接著利用錯合物1和有機分子反應：加入對位疊氮甲苯後除了得到五員環單核的Co(Nacnac)Dipp(1,4-p-Tol2N4) (8)外，亦可分離出另一含量較少的雙核產物[Co(Nacnac)Dipp(μ-N-p-Tol)]2 (9)。和偶氮苯反應會得到將氮-氮雙鍵輕微活化的(μ-κ1:κ1-PhNNPh)[Co(Nacnac)Dipp]2 (10)。除此之外，1亦能催化末端炔類進行三聚合環化反應；而與立體阻礙較大的炔類如三甲基矽乙炔反應，則會生成三鍵配位於鈷上的錯合物－Co(Nacnac)Dipp(η2-Me3SiCCH) (12)。和1,3,5,7-環辛四烯反應會得到文獻上罕見的C16H16Co2(Nacnac)Dipp2 (13)，其中環辛四烯二聚合形成七六七的融合環連接兩個鈷；但加入1,3,5-環庚三烯卻得到把橋接的甲苯分子取代的錯合物－(μ-η4:η4-C7H8)[Co(Nacnac)Dipp]2 (14)。
除此之外，我們使用立體阻礙較小的配基與釩反應得到(Nacnac)ArVCl2 (Ar = Dmp or Dep)，接著再以四氫呋喃為溶劑在氮氣環境下還原，卻得到沒有固定氮氣的錯合物－[(Nacnac)ArV]2 (15: Ar = Dmp; 16: Ar = Dep)。
另一方面，利用amidinate配基與無水的氯化亞鈷和碘化鎳反應分別得到(DippNC(H)NDipp)Co(μ-Cl)2Li(THF)2 (18)和(η1-DippNC(H)NDipp)NiI3Li(THF)2(OEt2)2 (22)，分別將其還原可分離出無前例低配位的雙核錯合物－[M(μ-η2-DippNC(H)NDipp)]2 (20: M = Co; 24: M = Ni)。除此之外若利用22加入1.5當量的還原劑，則可分離得到(μ-I)[Ni(μ-η2-DippNC(H)NDipp)]2 (23)。
Reduction of (Nacnac)DippCo(μ-Cl)2Li(THF)2 (Nacnac = HC(C(Me)NC6H3iPr2)2) by KC8 in toluene led to isolation of inverted-sandwich complex (μ-η2:η2-C7H8)[Co(Nacnac)Dipp]2 (1) in good yield. Then we found compound 1 able to activate small molecules and various organic functionalities, generating novel cobalt-containing complexes. Treatment of 1 with P4 afforded a P4-bridged compound (μ-η4:η4-P4)[Co(Nacnac)Dipp]2 (2), then we heat 2 for 4 days resulted in (μ-η3:η3-P3)[Co(Nacnac)Dipp]2 (3) with one phosphorus loss. Reaction with chalcogen elements furnished [Co(Nacnac)Dipp(μ-X)]2 (4: X = S; 5: X = Se) and [Co(Nacnac)Dipp(μ-TeH)]2 (6) respectively. While treatment of 1 with excess nitric oxide afforded diamagnetic compound Co(Nacnac)Dipp(NO)2 (7). Then we investigated the reactivity of 1 with organic functionalities. Reaction with p-TolN3 produced not only a five-membered-ring complex Co(Nacnac)Dipp(1,4-p-Tol2N4) (8), but a minor product [Co(Nacnac)Dipp(μ-N-p-Tol)]2 (9). Treatment of 1 with azobenzene led to isolation of (μ-κ1:κ1-PhNNPh)[Co(Nacnac)Dipp]2 (10), which had slightly activated N-N bond. Moreover, complex 1 can catalyze cyclotrimerization of alkynes and form C-C triple bond coordinated complexes while reaction with more steric hindered alkynes such as Me3SiCCH. The reaction of 1 with 1,3,5,7-cyclooctatetraene afforded novel compound C16H16Co2(Nacnac)Dipp2 (13), two COTs forming a new C16H16 skeleton containing 3 fused ring. While treatment with 1,3,5-cycloheptatiene produced (μ-η4:η4-C7H8)[Co(Nacnac)Dipp]2 (14) without dimerization of cycloheptatriene.
Moreover, we used less hindered ligand to synthesize vanadium complex (Nacnac)ArVCl2 (Ar = Dmp or Dep). Then we reduced it by KC8 in THF under N2 afforded [(Nacnac)ArV]2 (15: Ar = Dmp; 16: Ar = Dep) without N2 fixation.
Reaction of amidinate with anhydrous CoCl2 and NiI2 produced (DippNC(H)NDipp)Co(μ-Cl)2Li(THF)2 (18) and (η1-DippNC(H)NDipp)NiI3Li(THF)2(OEt2)2 (22) respectively. Reduction of 18 and 22 furnished unprecedented low-coordinate complex [M(μ-η2-DippNC(H)NDipp)]2 (20: M = Co; 24: M = Ni). Moreover, treatment of 22 with 1.5 equivalent KC8 produced mixed-valence (μ-I)[Ni(μ-η2-DippNC(H)NDipp)]2 (23).
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