臺灣博碩士論文加值系統

本論文主要以水楊醛、類做縮合反應，合成salen類Schiff-base配位基L1∼L9，(salen = N,N'-bis(salicylidenediaminato)ethylene )。再分別和錳、鐵離子反應，形成salen系列的錳(Ⅲ)、鐵(Ⅲ)錯合物。經元素分析、X-ray單晶繞射確定其成份組成與其分子結構。
在此實驗中，我們共得到四個單晶結構。分別為MnL1Cl、
MnL4Cl、MnL6Cl、FeL1Cl：
(1) MnL1Cl：為單斜晶系(Monoclinic)，晶格常數為a=18.131(4)A、
b=17.732(3)A、c=7.869(2)A，β=96.36(2)°，空間群為C2/c，Z=4，體積為2357.3(8)A3。
(2) MnL4Cl：為三斜晶系(Triclinic)，晶格常數a=9.1710(8)A、
b=11.5755(12)A、c=12.0468(8)A，α=107.284(7)°、β=99.150(6)°、γ=107.396(27)°空間群為P-1，Z=2，體積為1121.3(2)A3。
(3) MnL6Cl：為三斜晶系(Triclinic)，晶格常數為a=10.482(2)A、
b=10.774(2)A、c=11.654(2)A，α=106.16(2)°、β=96.36(2)°、γ=109.81(2)°，空間群為P-1，Z=2，體積為1158.6(4)A3。
(4) FeL1Cl：為單斜晶系(Monoclinic)，晶格常數為a=14.3706(6)A、
b=13.5500(5)A、c=14.9261(5)A，β=118.644(1)°，空間群為P21/n，Z=4，體積為2550.7(2)A3。
(L1=N,N'-bis(3-methoxy salicylidene)-1,2-cyclohexanediamine；L4= N,N'-bis(3-methoxy salicylidene)-1,2-phenylenediamine；L6=N,N'-bis(4,6-dimethoxy salicylidene)-1,2-propanediamine)
除了就單晶結構上的鍵結特性探討之外，其粉末之SQUID變溫磁化率測定，都遵循Curie-Weiss Law，唯低溫部份cT隨溫度下降而降低，解釋為錳(Ⅲ)、鐵(Ⅲ)之Jahn-Teller效應所引起之電子自旋相互作用(D)。另一方面，再將此類錯合物利用相同的氧化劑，對不同的烯類進行環氧化反應，可知錳錯合物的催化效果較鐵錯合物來的好。

The preparations, crystal structure, magnetic properties and their catalytic activity of the
olefin epoxidation of Iron(Ⅲ) and Manganese(Ⅲ) complexes with substitute salen's schiff-
base ligands(L1~L9). The described are investigated : (L1=N,N'-bis(3-methoxy salicylidene)-
1,2-cyclohexanediamine；L4= N,N'-bis(3-methoxy salicylidene)-1,2-phenylenediamine；
L6=N,N'-bis(4,6-dimethoxy salicylidene)-1,2-propanediamine).
X-ray crystallographic data for complexes MnL1Cl, MnL4Cl, MnL6Cl and FeL1Cl are
obtained as :
(1) MnL1Cl：Monoclinic, space group C2/c, Z=4, a=18.131(4)A、
b=17.732(3)A、c=7.869(2)A, β=96.36(2)°.
(2) MnL4Cl：Triclinic, space group P-1, Z=2, a=9.1710(8)A、b=11.5755(12)A、c=12.0468(8)A,α=107.284(7)°、β=99.150(6)°、γ=107.396(27)°.
(3) MnL6Cl：Triclinic, space group P-1, Z=2, a=10.482(2)A、b=10.774(2)A、c=11.654(2)A,α=106.16(2)°、β=96.36(2)°、γ=109.81(2)°.
(4) FeL1Cl： Monoclinic, space group P21/n, Z=4, a=14.3706(6)A、b=13.5500(5)A、c=14.9261(5)A，β=118.644(1)°.
Temperature dependence of magnetic susceptibility of these complexes are measured by
using SQUID magnetometer, and see the complexes show obey the Curie-Weiss law. The χT
rule decrease with decreasing temperature at low-temperature range is contributed to the
axial field symmetry of spin-spin interactions of Iron(Ⅲ) and Manganese(Ⅲ) ions in Jahn-
Teller distorted environments.
The epoxtation of trans-stilbene, methylstyrene with NaOCl , Iron(Ⅲ) and
Manganese(Ⅲ). The studies on catalytic activity of Iron(Ⅲ) and Manganese(Ⅲ) complexes
in olefins by NaOCl oxidant are found that the manganese(Ⅲ) are more active than the
Iron(Ⅲ) complexes.

中文摘要 Ⅰ
英文摘要 Ⅱ
圖目錄 Ⅲ
表目錄 Ⅵ
第一章 緒論
1-1 簡介 …………………………………… 1
1-2 氧原子轉換反應觸媒 ………………… 2
1-3 實驗目的 ……………………………… 7
第二章 實驗
2-1 試藥 …………………………………… 8
2-2 錳錯合物之合成 …………………….. 10
2-3 鐵錯合物之合成 …………………….. 11
2-4 似催化媒活性反應之測量 ………….. 14
2-5 物理性質之測定 …………………….. 15
第三章 結果與討論
3-1 一般性質 …………………………….. 16
3-2 IR光譜 ………………………………. 19
3-3 晶體結構 …………………………….. 20
3-4 磁性 ………………………………….. 45
3-5 錯合物催化環氧化反應之探討 …….. 72
第四章 結論 ……………………………………….... 75
第五章 參考文獻 …………………………………… 77
附錄 A …………………………………………………. 81
附錄 B …………………………………………………. 94

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