新型铜（II）诱导卟吩原衍生物的形成：三吡唑基三脚架配体的铜（II）和钴（III）配合物的卟吩原配合物的X射线结构、光谱和电化学研究

Novel copper(II) induced formation of a porphyrinogen derivative: X-ray structural, spectroscopic, and electrochemical studies of porphyrinogen complexes of Cu(II) and Co(III) complex of a trispyrazolyl tripodal ligand.

作者信息

Paul Sachindranath, Barik Anil Kumar, Peng Shie Ming, Kar Susanta Kumar

机构信息

Department of Chemistry, SreeChaitanya College, Habra, North 24 Parganas, West Bengal, India.

出版信息

Inorg Chem. 2002 Nov 4;41(22):5803-9. doi: 10.1021/ic0112185.

DOI:10.1021/ic0112185

PMID:12401086

Abstract

Copper(II) complexes of a novel pyrazole containing porphyrinogen and cobalt(III) and zinc(II) complexes of a pyrazole containing tripodal ligand having N-donor atoms have been investigated. 5-Methyl-3-formylpyrazole (MPA) on reaction with copper(II) nitrate or perchlorate in the presence of tris(2-aminoethyl)amine (tren) forms novel pyrazole-based porphyrinogen complexes Cu(T(3)-porphyrinogen)(H(2)O)(2) (1a) and Cu(T(3)-porphyrinogen)(H(2)O)(2) (1b) where T(3)-porphyrinogen is 1,6,11,16-tetraaza-5,10,15,20-tetrahydroxy-2,7,12,17-tetramethylporphyrinogen. The same products are also obtained when tren is replaced by triethylamine. By contrast, the reaction between MPA, tren, and cobalt(II) perchlorate produces the cobalt(III) complex [Co(HMPz(3)tren)]ClO(4) (2) derived from the tripodal Schiff base tris[4-(3-(5-methyl-pyrazolyl)-3-aza-3-butenyl]amine (H(3)MPz(3)tren). The X-ray crystal structures of the copper(II) complexes (1a and 1b) and the cobalt(III) complex (2) have been determined. The structures show distorted square pyramidal coordination environments for 1a and 1b with the water molecule occupying the apical site, while for complex 2 a distorted octahedral geometry is obtained. Data for 1a follow: a = 19.476(3) A, b = 9.4116(8) A, c = 14.204(3) A; alpha = 90 degrees = gamma, beta = 107.58(2) degrees; V = 2482.0(7) A(3), Z = 4. Data for 1b follow: a = 20.967(3) A, b = 9.1563(18) A, c = 14.858(4) A; alpha = 90 degrees = gamma, beta = 108.44(3) degrees; V = 2706.0(10) A(3), Z = 4. Data for 2 follow: a = 21.293(3) A, b = 12.724(2) A, c = 19.777(4) A; alpha = 90 degrees = gamma, beta = 93.03(2) degrees; V = 5350.6(15) A(3), Z = 8. All three complexes crystallize in the monoclinic crystal system with the C2/c space group. The complexes are further characterized by UV-vis, IR, EPR, and electrochemical studies.

摘要

研究了一种含新型吡唑的卟啉原的铜（II）配合物以及一种含吡唑的具有氮供体原子的三脚架配体的钴（III）和锌（II）配合物。5-甲基-3-甲酰基吡唑（MPA）在三（2-氨基乙基）胺（tren）存在下与硝酸铜（II）或高氯酸铜（II）反应，形成新型的基于吡唑的卟啉原配合物Cu(T(3)-卟啉原)(H₂O)₂ (1a) 和 Cu(T(3)-卟啉原)(H₂O)₂ (1b)，其中T(3)-卟啉原是1,6,11,16-四氮杂-5,10,15,20-四羟基-2,7,12,17-四甲基卟啉原。当tren被三乙胺取代时，也能得到相同的产物。相比之下，MPA、tren和高氯酸钴（II）之间的反应生成了源自三脚架席夫碱三[4-(3-(5-甲基-吡唑基)-3-氮杂-3-丁烯基]胺（H₃MPz₃tren）的钴（III）配合物[Co(HMPz₃tren)]ClO₄ (2)。已测定了铜（II）配合物（1a和1b）和钴（III）配合物（2）的X射线晶体结构。结构表明1a和1b具有扭曲的四方锥配位环境，水分子占据顶端位置，而配合物2具有扭曲的八面体几何结构。1a的数据如下：a = 19.476(3) Å，b = 9.4116(8) Å，c = 14.204(3) Å；α = 90° = γ，β = 107.58(2)°；V = 2482.0(7) Å³，Z = 4。1b的数据如下：a = 20.967(3) Å，b = 9.1563(18) Å，c = 14.858(4) Å；α = 90° = γ，β = 108.44(3)°；V = 2706.0(10) Å³，Z = 4。2的数据如下：a = 21.293(3) Å，b = 12.724(2) Å，c = 19.777(4) Å；α = 90° = γ，β = 9

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新型铜（II）诱导卟吩原衍生物的形成：三吡唑基三脚架配体的铜（II）和钴（III）配合物的卟吩原配合物的X射线结构、光谱和电化学研究

Novel copper(II) induced formation of a porphyrinogen derivative: X-ray structural, spectroscopic, and electrochemical studies of porphyrinogen complexes of Cu(II) and Co(III) complex of a trispyrazolyl tripodal ligand.

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