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铜(I)-嘌呤-膦配合物。[Cu(2)(μ-HL(1))(2)(μ-dppm)(η(1)-dppm)(2)]和{[Cu(3)(μ(3)-Cl)(2)(μ-dppm)(3)][Cu(HL(2))(2)]}的合成与分子结构(H(2)L(1)=8-巯基茶碱,H(2)L(2)=8-乙基-3-甲基黄嘌呤)

Copper(I)-Purine-Phosphine Complexes. Syntheses and Molecular Structures of [Cu(2)(&mgr;-HL(1))(2)(&mgr;-dppm)(eta(1)-dppm)(2)] and {[Cu(3)(&mgr;(3)-Cl)(2)(&mgr;-dppm)(3)][Cu(HL(2))(2)]} (H(2)L(1) = 8-Mercaptotheophylline and H(2)L(2) = 8-Ethyl-3-methylxanthine).

作者信息

Colacio E., Cuesta R., Moreno J. M.

机构信息

Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain.

出版信息

Inorg Chem. 1997 Mar 12;36(6):1084-1087. doi: 10.1021/ic960928l.

Abstract

The syntheses and molecular structures of two novel polynuclear copper(I)-purine-phosphine complexes are reported. The first one is a dinuclear [Cu(2)(&mgr;-HL(1))(2)(&mgr;-dppm)(eta(1)-dppm)(2)] complex (H(2)L(1) is 8-mercaptotheophylline). The compound crystallizes in the triclinic system, space group P&onemacr;, with cell constants a = 12.342(5) Å, b = 15.255(5) Å, c = 24.972(5) Å, alpha = 74.31(2) degrees, beta = 78.62(2) degrees, gamma = 72.51(2) degrees, and Z = 2. The structure of this complex exhibits as the most important feature the simultaneous presence of eta(1)-terminal and eta(2)-bridging dppm ligands, which is first here described for a copper complex. This complex is also of interest because of its reversible photochromic behavior in the solid state. The second compound is an ionic {[Cu(3)(&mgr;(3)-Cl)(2)(&mgr;-dppm)(3)][Cu(HL(2))(2)]} complex (H(2)L(2) is 8-ethyl-3-methylxanthine), which crystallizes in the monoclinic system, space group P2(1)/n, with cell constants a = 15.829(6) Å, b = 22.801(7) Å, c = 28.569(6) Å, beta = 97.65(4) degrees, and Z = 6. The structure of this complex consists of trinuclear copper(I) cations and mononuclear Cu(purine)(2) anions, exhibiting a linear stereochemistry. As far as we know, this compound represents the first example of a copper(I)-purine complex whose structure has been determined by X-ray crystallography.

摘要

报道了两种新型多核铜(I)-嘌呤-膦配合物的合成及其分子结构。第一种是双核[Cu₂(μ-HL₁)₂(μ-dppm)(η¹-dppm)₂]配合物(H₂L₁为8-巯基茶碱)。该化合物结晶于三斜晶系,空间群为P-1,晶胞参数a = 12.342(5) Å,b = 15.255(5) Å,c = 24.972(5) Å,α = 74.31(2)°,β = 78.62(2)°,γ = 72.51(2)°,Z = 2。该配合物结构的最重要特征是同时存在η¹-末端和η²-桥连的dppm配体,这在此处首次针对铜配合物进行描述。该配合物因其在固态下的可逆光致变色行为也备受关注。第二种化合物是离子型{[Cu₃(μ₃-Cl)₂(μ-dppm)₃][Cu(HL₂)₂]}配合物(H₂L₂为8-乙基-3-甲基黄嘌呤),它结晶于单斜晶系,空间群为P2₁/n,晶胞参数a = 15.829(6) Å,b = 22.801(7) Å,c = 28.569(6) Å,β = 97.65(4)°,Z = 6。该配合物结构由三核铜(I)阳离子和单核[Cu(嘌呤)₂]⁻阴离子组成,呈现线性立体化学。据我们所知,该化合物是首个其结构已通过X射线晶体学确定的铜(I)-嘌呤配合物实例。

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