Nairn Alison K, Archibald Stephen J, Bhalla Rajiv, Gilbert Bruce C, Maclean Elizabeth J, Teat Simon J, Walton Paul H
Department of Chemistry, University of York, Heslington, York, UK YO10 5DD.
Dalton Trans. 2006 Jan 7(1):172-6. doi: 10.1039/b512296c. Epub 2005 Oct 28.
Reaction of Cu(BF(4))(2).6H(2)O with the N(3)O(2) donor ligand H(2)L (where H(2)L = N-benzyl-N',N''-di-tert-butyl-disalicyl-triaminocyclohexane) results in the formation of a novel Cu(II)L complex, 1. X-Ray crystallography of it shows the Cu(II) centre coordinated by two phenolate oxygens and two imine nitrogens in a distorted square plane with an elongated bond to the amine nitrogen (2.512 A) in the axial position. EPR spectroscopy gives g values of g(1) = 2.277, g(2) = 2.100, g(3) = 2.025, and A(1) = 15.6 mT which are consistent with the distorted square pyramidal coordination environment determined from the X-ray structure. UV/visible and electrochemical analysis of shows that it undergoes two reversible processes assigned to the successive oxidation of the phenolate oxygens to phenoxyl radicals, the first at E((1/2)) = 0.89 V (DeltaE = 81 mV, vs. Ag/AgCl) and the second at E((1/2)) = 1.13V (DeltaE = 84 mV, vs. Ag/AgCl). Chemical oxidation results in the formation of a species, assigned as 1(.) which is EPR silent due to antiferromagnetic coupling between the Cu(II) centre and the bound phenoxyl radical. The oxidised species catalyses the oxidation of benzyl alcohol to benzaldehyde.
Cu(BF₄)₂·6H₂O 与 N₃O₂ 供体配体 H₂L（其中 H₂L = N-苄基-N',N''-二叔丁基-二水杨基-三氨基环己烷）反应生成一种新型的 Cu(II)L 配合物 1。其 X 射线晶体学表明，Cu(II) 中心在一个扭曲的平面内由两个酚氧原子和两个亚胺氮原子配位，轴向位置与胺氮原子有一个拉长的键（2.512 Å）。电子顺磁共振光谱给出的 g 值为 g₁ = 2.277、g₂ = 2.100、g₃ = 2.025，以及 A₁ = 15.6 mT，这与由 X 射线结构确定的扭曲四方锥配位环境一致。紫外/可见光谱和电化学分析表明，它经历了两个可逆过程，这两个过程归因于酚氧原子连续氧化为苯氧自由基，第一个过程的 E(1/2) = 0.89 V（ΔE = 81 mV，相对于 Ag/AgCl），第二个过程的 E(1/2) = 1.13 V（ΔE = 84 mV，相对于 Ag/AgCl）。化学氧化导致形成一种物种，被指定为 1(·)，由于 Cu(II) 中心与结合的苯氧自由基之间的反铁磁耦合，该物种的电子顺磁共振信号沉默。氧化后的物种催化苄醇氧化为苯甲醛。
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