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 Trispyrazol
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- 作者：Sachindranath Paul ; Anil Kumar Barik ; Shie Ming Peng ; and Susanta Kumar Kar
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：November 4, 2002
- 年：2002
- 卷：41
- 期：22
- 页码：5803 - 5809
- 全文大小：126K
- 年卷期：v.41,no.22(November 4, 2002)
- ISSN：1520-510X
文摘
Copper(II) complexes of a novel pyrazole containing porphyrinogen and cobalt(III) and zinc(II) complexes of apyrazole 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 novelpyrazole-based porphyrinogen complexes [Cu(T3-porphyrinogen)(H2O)](NO3)2 (1a) and [Cu(T3-porphyrinogen)(H2O)](ClO4)2 (1b) where T3-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 betweenMPA, tren, and cobalt(II) perchlorate produces the cobalt(III) complex [Co(HMPz3tren)]ClO4 (2) derived from thetripodal Schiff base tris[4-(3-(5-methyl-pyrazolyl)-3-aza-3-butenyl]amine (H3MPz3tren). The X-ray crystal structuresof the copper(II) complexes (1a and 1b) and the cobalt(III) complex (2) have been determined. The structuresshow distorted square pyramidal coordination environments for 1a and 1b with the water molecule occupying theapical site, while for complex 2 a distorted octahedral geometry is obtained. Data for 1a follow: a = 19.476(3) Å,b = 9.4116(8) Å, c = 14.204(3) Å; 
= 90
= 
, 
= 107.58(2); V = 2482.0(7) Å3, Z = 4. Data for 1b follow:a = 20.967(3) Å, b = 9.1563(18) Å, c = 14.858(4) Å; = 90 = , = 108.44(3); V = 2706.0(10) Å3, Z =4. Data for 2 follow: a = 21.293(3) Å, b = 12.724(2) Å, c = 19.777(4) Å; = 90 = , = 93.03(2); V =5350.6(15) Å3, 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.
= 90 = , = 107.58(2); V = 2482.0(7) Å3, Z = 4. Data for 1b follow:a = 20.967(3) Å, b = 9.1563(18) Å, c = 14.858(4) Å; = 90 = , = 108.44(3); V = 2706.0(10) Å3, Z =4. Data for 2 follow: a = 21.293(3) Å, b = 12.724(2) Å, c = 19.777(4) Å; = 90 = , = 93.03(2); V =5350.6(15) Å3, 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.