A new bis(1-naphthylimino)acenaphthene compound and its Pd(II) and Zn(II) complexes:: Synthesis, characterization, solid-state structures and density functional theory studies on the syn and anti isomers
A new bis(1-naphthylimino)acenaphthene compound and its Pd(II) and Zn(II) complexes:: Synthesis, characterization, solid-state structures and density functional theory studies on the syn and anti isomers
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DOI：
10.1021/ic800790u
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发表时间：
2008-09-01
影响因子：
4.6
通讯作者：
Lodeiro, Carlos
中科院分区：
文献类型：
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作者：
Rosa, Vitor;Aviles, Teresa;Lodeiro, Carlos
合成了一种新的刚性双齿配体双(1-萘亚氨基)庚，L1，及其锌(II)、钯(II)配合物[ZnCl2(L1)]，1，[PdCl2(L1)]，2。L1是用“模板法”合成的，在氯化锌的存在下，1-萘胺和并苯二酮反应，得到1，进一步脱金属。1-萘胺与1-萘醌和PdCl2反应生成二氯化物双(1-萘基)2-萘二亚胺钯，L1，1和2为正反异构体的混合物。化合物2也是通过PdCl2在乙腈中回流活化，然后加入L1反应得到的，通过这种路线也得到了正反异构体的混合物，但反应速度不同。用单晶X-射线衍射法测定了化合物L1和化合物2的异构体的固态结构。通过元素分析、基质辅助激光解吸电离飞行时间质谱学、IR、UV-Vis、H-1、C-13和H-1-H-1相关谱、H-1-C-13异核单量子相干谱、H-1-C-13异核单量子相干-全相关谱和H-1-H-1核Overhauser效应核磁共振谱对所有化合物进行了表征。密度泛函理论研究表明，[PdCl2(Bian)]的两种构象都是等能的，都可以从实验上得到。然而，我们可以预测，异构化过程在正方形平面络合物中是不可能的，但对于自由配体是可能的。这两种异构体的分子几何构型非常相似，只有萘基的取向可能不同。
A new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, L1, and its Zn(II) and Pd(II) complexes [ZnCl2(L1)], 1, and [PdCl2(L1)], 2, were synthesized. L1 was prepared by the "template method", reacting 1-naphthyl amine and acenaphthenequinone in the presence of ZnCl2, giving 1, which was further demetallated. Reaction of 1-naphthyl amine with acenaphthenequinone and PdCl2 afforded dichloride bis(1-naphthyl)acenaphthenequinonediimine palladium, 2. L1, 1, and 2 were obtained as a mixture of syn and anti isomers. Compound 2 was also obtained by the reaction of PdCl2 activated by refluxing it in acetonitrile followed by the addition of L1; by this route also a mixture of syn and anti isomers was obtained, but at a different rate. The solid-state structures of L1 and the anti isomer of compound 2 have been determined by single-crystal X-ray diffraction. All compounds have been characterized by elemental analyses; matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry; IR; UV-vis; H-1, C-13, and H-1-H-1 correlation spectroscopy; H-1-C-13 heteronuclear single quantum coherence; H-1-C-13 heteronuclear single quantum coherence-total correlation spectroscopy; and H-1-H-1 nuclear Overhauser effect spectrometry NMR spectroscopies when applied. Density functional theory studies showed that both conformers for [PdCl2(BIAN)] are isoenergetic, and they can both be obtained experimentally. However, we can predict that the isomerization process is not available in a square-planar complex, but it is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected.