中文摘要
本研究以雙(2-啶甲基)醚(bpmo)為主要的配子，共合成四個系列二價銅錯合物：
(1)[Cu(bpmo)(NN)](ClO4)2：其中NN包括2,2’-聯啶(bipy)、1,10-二氮雜菲(phen)、N,N,N’,N’-四甲基乙二胺(tmen)。
(2)[Cu(bpmo)(N)](ClO4)2：其中N包括4-甲基啶(4Mepy)、N-甲基咪唑(NMeIm)、2-甲基醇啶(pyCH2OH)。
(3)[Cu(bpmo)(X)2]：其中X包括Br、Cl。
(4)[Cu(bpmo)2](ClO4)2。
利用元素分析、X光結構解析、紅外光光譜、電子吸收光譜、電子順磁共振光譜及可見光高斯交疊解析等，完成錯合物的結構鑑定及鍵結性質的探討。
目前已完成X光單晶結構解析的二價銅錯合物有：
(a) fac-[Cu(bpmo)(bipy)(ClO4)](ClO4)
屬三斜晶系(Triclinic)，空間群為P-1，晶格常數a = 8.8186(1)Å，b = 10.6142(2)Å，c = 15.0084(4)Å，a = 88.644(1)º，b = 75.102(1)º，g = 67.897(2)º，每單位晶格內有2個分子(Z = 2)，精算值R = 0.047，Rw = 0.090。
(b) fac-[Cu(bpmo)(phen)](ClO4)2
屬單斜晶系(Monoclinic)，空間群為C2/m，晶格常數a = 19.0002(4)Å，b = 10.9264(3)Å，c = 16.8516(4)Å，a = 90.00º，b = 117.310(2)º，g = 90.00º，每單位晶格內有4個分子(Z = 4)，精算值R = 0.141，Rw = 0.267。
(c) fac-[Cu(bpmo)(tmen)(CH3CN)](ClO4)2(CH3CN)
屬單斜晶系(Monoclinic)，空間群為P21/n，晶格常數a = 8.308(2)Å，b = 17.208(5)Å，c = 21.242(8)Å，a = 90.00º，b = 100.07(3)º，g = 90.00º，每單位晶格內有4個分子(Z = 4)，精算值R = 0.109，Rw = 0.141。
(d) mer-[Cu(bpmo)(4Mepy)(ClO4)](ClO4)(H2O)
三斜晶系(Triclinic)，空間群為P-1，晶格常數a = 8.3778(1)Å，b = 8.6333(2)Å，c = 18.3404(5)Å，a = 76.641(1)º，b = 83.815(1)º，g = 62.407(1)º，每單位晶格內有2個分子(Z = 2)，精算值R = 0.102，Rw = 0.256。
(e) mer-[Cu(bpmo)(NMeIm)(ClO4)](ClO4)
三斜晶系(Triclinic)，空間群為P-1，晶格常數a = 8.388(8)Å，b = 8.693(3)Å，c = 16.599(3)Å，a = 78.58(2)º，b = 82.68(5)º，g = 62.86(5)º，每單位晶格內有2個分子(Z = 2)，精算值R = 0.064，Rw = 0.066。
(f) mer-[Cu(bpmo)(Br)2]
屬單斜晶系(Monoclinic)，空間群為P21/n，晶格常數a = 8.2448(2)Å，b = 12.8300(3)Å，c = 13.1692(4)Å，a = 90.00º，b = 92.458(1)º，g = 90.00º，每單位晶格內有4個分子(Z = 4)，精算值R = 0.049，Rw = 0.102。
(g) mer-[Cu(bpmo)(Cl)2]
屬單斜晶系(Monoclinic)，空間群為P21/n，晶格常數a = 8.1618(2)Å，b = 12.5669(3)Å，c = 12.8289(4)Å，a = 90.00º，b = 91.622(1)º，g = 90.00º，每單位晶格內有4個分子(Z = 4)，精算值R = 0.031，Rw = 0.063。
由系列(1)及系列(4)錯合物的溶液態可見光光譜高斯解析結果，
顯示三牙基配子bpmo為π-acceptor配位基。
bpmo銅錯合物的反應性研究，探討配子bpmo在室溫下與一價銅形成錯合物後與氧氣的反應，發現配子bpmo所形成的一價銅錯合物，可將2,4-二-特-丁基苯酚催化氧化成3,3¢,5,5¢-四-特-丁基-2,2¢-聯苯酚，推測其反應過程中可能有形成bis(m-oxo)dicopper(Ⅲ)的錯合物。

Abstract
Four types of copper(II) complexes of bis(2-pyridylmethyl)ether
(bpmo) have been prepared.
(1)[Cu(bpmo)(NN)](ClO4)2, where NN stands for 2,2’-bipyridine (bipy), 1,10-phenanthroline (phen), and N,N,N’,N’-tetramethylethylene-
diamine (tmen).
(2)[Cu(bpmo)(N)](ClO4)2, where N represents 4-methylpyridine (4Mepy), N-methylimidazole (NMeIm), and 2-(Hydroxymethyl)pyridine
(pyCH2OH).
(3)[Cu(bpmo)(X)2], where X is Br and Cl.
(4)[Cu(bpmo)2](ClO4)2.
These complexes have been characterized by elemental analyses, IR, UV-VIS, and EPR spectroscopic measurements, and single-crystal X-ray diffraction. The crystal data of the complexes are described below:
(a) fac-[Cu(bpmo)(bipy)(ClO4)](ClO4)
Triclinic, space group P-1, a = 8.8186(1)Å, b = 10.6142(2)Å, c = 15.0084(4)Å, a = 88.644(1)º, b = 75.102(1)º, g = 67.897(2)º, Z = 2, R = 0.047, Rw = 0.090.
(b) fac-[Cu(bpmo)(phen)](ClO4)2
Monoclinic, space group C2/m, a = 19.0002(4)Å, b = 10.9264(3)Å, c = 16.8516(4)Å, a = 90.00º, b = 117.310(2)º, g = 90.00º, Z = 4, R = 0.141, Rw = 0.267.
(c) fac-[Cu(bpmo)(tmen)(CH3CN)](ClO4)2(CH3CN)
Monoclinic, space group P21/n, a = 8.308(2)Å, b = 17.208(5)Å, c = 21.242(8)Å, a = 90.00º, b = 100.07(3)º, g = 90.00º, Z = 4, R = 0.110, Rw =0.312.
(d) mer-[Cu(bpmo)(4Mepy)(ClO4)](ClO4)(H2O)
Triclinic, space group P-1, a = 8.3778(1)Å, b = 8.6333(2)Å, c = 18.3404(5)Å, a = 76.641(1)º, b = 83.815(1)º, g = 62.407(1)º, Z = 2, R = 0.102, Rw = 0.256.
(e) mer-[Cu(bpmo)(NMeIm)(ClO4)](ClO4)
Triclinic, space group P-1, a = 8.388(8)Å, b = 8.693(3)Å, c = 16.599(3)Å, a = 78.58(2)º, b = 82.68(5)º, g = 62.86(5)º, Z = 2, R = 0.064, Rw = 0.066.
(f) mer-[Cu(bpmo)(Br)2]
Monoclinic, space group P21/n, a = 8.2448(2)Å, b = 12.8300(3)Å, c = 13.1692(4)Å, a = 90.00º, b = 92.4581(11)º, g = 90.00º, Z = 4, R = 0.049, Rw = 0.102.
(g) mer-[Cu(bpmo)(Cl)2]
Monoclinic, space group P21/n, a = 8.1618(2)Å, b = 12.5669(3)Å, c = 12.8289(4)Å, a = 90.00º, b = 91.622(1)º, g = 90.00º, Z = 4, R = 0.031, Rw = 0.063.
Based on Gaussian analyses of the solution LF spectra of the type (1) and (2) complexes, the bpmo binds to copper as a p-acceptor.
The reactions of O2 with the Cu(I) complex, [Cu(bpmo)]+, at room temperature have been investigated. The reaction of 2,4-di-tert-butyl-
phenol with O2 in the presence of [Cu(bpmo)]+ yields the dimeric product, 3,3¢,5,5¢-tetra-tert-butyl-2,2¢-biphenol, suggesting the formation of the bis(m-oxo)dicopper(Ⅲ) intermediate.

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