Anomalous solution esr spectra observed for halogenocopper (II) complexes with tripodlike ligands
Anomalous solution esr spectra observed for halogenocopper (II) complexes with tripodlike ligands
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观察到具有三脚架状配体的卤代铜 (II) 配合物的反常溶液 ESR 光谱
DOI：
10.1021/ic00281a022
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发表时间：
1988
影响因子：
4.6
通讯作者：
Kazuhiro Takahashi
中科院分区：
文献类型：
--
作者：
Y. Nishida;Kazuhiro Takahashi
卤代铜(II)与三脚状配体(L)，[Cu(L)X]Y(X=Br“和；Y=C1G4和Pf6)在室温下的溶液ESR谱中出现4条以上的超精细线(5-9条线)。这归因于铜(II)离子的未成对电子与铜原子(63，65Cu，i=123/2)和卤素原子(79，81Br，i=3/2；127I，i=1/2)的核自旋相互作用。三个化合物[Cu(N3S)N3]C104(1)、[Cu(N3S)BR]C104(2)和[Cu(N2S2P)I]C104(3)的晶体结构测定证实了上述讨论，其中N3S和N2S2P分别代表双(2-吡啶甲基)(2-(甲硫基)乙基)胺和双(2-(甲硫基)乙基)(2-吡啶甲基)胺。晶胞参数：1，空间群P2，/a，a=16.316(5)A，6=8.379(1)A，c=14.409(2)A，？=100.69(2)：2，空间群P2，/o，a=14.600(7)A，b=17.155(8)A，c=7.686(1)A，？3，空间群P2，/n，a=17.292(3)A，b=14.411(2)A，c=7.8202(7)A，？=100.29(1)。配合物1具有四方锥体结构，硫醚基的硫原子位于正方形平面的顶端，叠氮离子位于配位球面上。化合物2的结构性质与化合物1基本相同，不同之处在于化合物2中的N3离子被Br3离子取代。配合物1在溶液ESR谱中有4条超精细谱线，而化合物2有5条超精细谱线，这表明在方面角的Br2离子的存在导致了异常的ESR谱。配合物3具有扭曲的三角双锥结构，其中铜(II)离子dz2轨道上的未配对电子可以通过成键与碘原子相互作用。在X=I“系列中，随着配体从三(2-甲硫基乙基)胺到三(2-吡啶甲基)胺的变化，超精细线由九条减少到七条。X=BR‘络合物也有类似的情况。假设未成对的电子与卤素原子的核自旋之间的相互作用取决于类三脚架配体L的性质，从而成功地解释了这些现象。
Halogenocopper (II) complexes with tripodlike ligands (L),[Cu (L) X] Y (X= Br" and; Y= C1G4 and PF6), showed more than four hyperfine lines (5-9 lines) in the solution ESR spectra at room temperature. This was attributed to the interaction between the unpaired electron of the copper (II) ion and the nuclear spins of both the copper atom (63, 65Cu, I= 123/2) and the halogen atom (79, 81Br,/= 3/2; 127I, I=$/2). The above discussion was confirmed by the crystal structure determination of three compounds,[Cu (N3S) N3] C104 (1),[Cu (N3S) Br] C104 (2), and [Cu (N2S2P) I] C104 (3), where N3S and N2S2P represent bis (2-pyridylmethyl)(2-(methylthio) ethyl) amine and bis (2-(methylthio) ethyl)(2-pyridylmethyl) amine, respectively. Crystal data: 1, space group P2,/a, a= 16.316 (5) A, 6= 8.379 (1) A, c= 14.409 (2) A, ß= 100.69 (2); 2, space group P2,/o, a= 14.600 (7) A, b= 17.155 (8) A, c= 7.686 (1) A, ß= 94.89 (2); 3, space group P2,/n, a= 17.292 (3) A, b= 14.411 (2) A, c= 7.8202 (7) A, ß= 100.29 (1). Complex 1 has a square-pyramidal structure; the sulfur atom of the thioether group is at the apical position of the square plane, and the azide ion is in the plane of the coordination sphere. The structural properties of 2 are essentially the same as those of 1 except that theN3 ionin 1 is replaced byBr" ion in 2. Complex 1 shows four hyperfine lines in the solution ESR spectrum, whereas five lines are observed for compound 2, indicating that thepresence of Br" ion at the corner of the square plane causes the unusual ESR spectrum. Complex 3 hasa distorted-trigonal-bipyramidal structure where the unpaired electron in the dz2 orbital of the copper (II) ion can interact with the iodine atom through-bonding. In the series of X= I" complexes, hyperfine lines decrease from nine to seven with the variation of ligand from tris (2-(methylthio) ethyl) amine to tris (2-pyridylmethyl) amine. A similar situation was alsofound for the X= Br'complexes. These were successfully explained on the assumption that the interaction between the unpaired electron and the nuclear spin of the halogen atom is dependent on the character of the tripodlike ligand L.