H2O2-reactivity of copper(II) complexes supported by tris[(pyridin-2-yl)methyl]amine ligands with 6-phenyl substituents.
H2O2-reactivity of copper(II) complexes supported by tris[(pyridin-2-yl)methyl]amine ligands with 6-phenyl substituents.
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DOI：
10.1021/ic801568g
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发表时间：
2008-11
影响因子：
4.6
通讯作者：
Atsushi Kunishita;M. Kubo;Hirohito Ishimaru;T. Ogura;H. Sugimoto;S. Itoh
中科院分区：
文献类型：
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作者：
Atsushi Kunishita;M. Kubo;Hirohito Ishimaru;T. Ogura;H. Sugimoto;S. Itoh
本文研究了一系列三甲基溴化铵支载的铜配合物的结构和H（2）O（2）-反应活性。在吡啶供体基团的6-位上具有苯基的[（吡啶-2-基）甲基]胺（TPA）衍生物[（6-苯基吡啶-2-基）甲基]二[（吡啶-2-基）甲基]胺（Ph（1）TPA），双[（6-苯基吡啶-2-基）甲基][（吡啶-2-基）甲基]胺（Ph（2）TPA），tris[对6-苯基吡啶-2-基）甲基]胺（Ph（3）TPA）的芳香取代基进行了系统的研究对TPA配体体系配位化学的影响。X射线晶体学分析表明，[Cu（II）（TPA）（CH（3）CN）]（ClO（4））（2）（CuTPA）和[Cu（II）（Ph（3）TPA）（CH（3）CN）]（ClO（4））（2）（3）具有三角双锥结构，而[Cu（II）（Ph（1）TPA）（CH（3）CN）]（ClO（4））（2）（1）显示轻微扭曲的四方锥结构，[Cu（II）（Ph（2）TPA）（CH（3）CN）]（ClO（4））（2）（2）具有三角双锥和正方锥之间的中间结构。另一方面，UV-vis和ESR数据表明，所有的铜（II）配合物在溶液中具有类似的三角双锥结构。测得CuTPA、1、2和3的氧化还原电位分别为E（1/2）=-0.34、-0.28、-0.16和-0.04 mV vs Ag/阿尼奥（3）。表明每个6-Ph基团的引入导致E（1/2）正移约0.1V。在Cu（II）之间发现了H（2）O（2）-反应性的显著差异。配合物即，CuTPA和1分别得到单核铜（II）-氢过氧络合物CuTPA-OOH和1-OOH，而络合物2提供双（μ-氧代）二铜（III）络合物2-氧代。另一方面，铜（II）络合物3被还原成相应的铜（I）络合物3（红色）。根据H（2）O（2）-反应活性、X-射线结构和铜（II）配合物的氧化还原电位，详细讨论了6-Ph的取代基效应。
The structure and H(2)O(2)-reactivity of a series of copper(II) complexes supported by tris[(pyridin-2-yl)methyl]amine (TPA) derivatives having a phenyl group at the 6-position of pyridine donor group(s) [(6-phenylpyridin-2-yl)methyl]bis[(pyridin-2-yl)methyl]amine (Ph(1)TPA), bis[(6-phenylpyridin-2-yl)methyl][(pyridin-2-yl)methyl]amine (Ph(2)TPA), and tris[(6-phenylpyridin-2-yl)methyl]amine (Ph(3)TPA) have systematically been examined to get insights into the aromatic substituent (6-Ph) effects on the coordination chemistry of TPA ligand system. The X-ray crystallographic analyses have revealed that [Cu(II)(TPA)(CH(3)CN)](ClO(4))(2) (CuTPA) and [Cu(II)(Ph(3)TPA)(CH(3)CN)](ClO(4))(2) (3) exhibit a trigonal bipyramidal structure, whereas [Cu(II)(Ph(1)TPA)(CH(3)CN)](ClO(4))(2) (1) shows a slightly distorted square pyramidal structure and [Cu(II)(Ph(2)TPA)(CH(3)CN)](ClO(4))(2) (2) has an intermediate structure between trigonal bipyramidal and square pyramidal. On the other hand, the UV-vis and ESR data have suggested that all the copper(II) complexes have a similar trigonal bipyramidal structure in solution. The redox potentials of CuTPA, 1, 2, and 3 have been determined as E(1/2) = -0.34, -0.28, -0.16, and -0.04 mV vs Ag/AgNO(3), respectively, demonstrating that introduction of each 6-Ph group causes positive shift of E(1/2) about 0.1 V. Notable difference in H(2)O(2)-reactivity has been found among the copper(II) complexes. Namely, CuTPA and 1 afforded mononuclear copper(II)-hydroperoxo complexes CuTPA-OOH and 1-OOH, respectively, whereas complex 2 provided bis(mu-oxo)dicopper(III) complex 2-oxo. On the other hand, copper(II) complex 3 was reduced to the corresponding copper(I) complex 3(red). On the basis of the H(2)O(2)-reactivity together with the X-ray structures and the redox potentials of the copper(II) complexes, the substituent effects of 6-Ph are discussed in detail.