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Hydrothermal Synthesis of Two Mixed‐Valence Copper Complexes with Mixed Ligands
Author(s) -
He Xiang,
Lu CanZhong
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300417
Subject(s) - triclinic crystal system , monoclinic crystal system , copper , chemistry , crystallography , phenanthroline , valence (chemistry) , crystal structure , hydrothermal circulation , ligand (biochemistry) , stereochemistry , organic chemistry , biochemistry , receptor , seismology , geology
Hydrothermal reactions of copper salts with fumaric acid, 1, 10‐phenanthroline or 2, 2‐bipyridine in basic aqueous solution gave rise to two mixed‐valence copper complexes [Cu 4 (ophen) 4 (fum)] ( 1 ) and [Cu 4 (obipy) 4 (fum)]·6H 2 O ( 2 ) (fum = fumarate dianion, Hophen = 2‐hydroxy‐1, 10‐phenanthroline and Hobpy = 6‐hydroxy‐2, 2′‐bipyridine), which were characterized by single crystal X‐ray analysis. [Cu 4 (ophen) 4 (fum)] (1) crystallizes in the monoclinic space group P2 1 /n, with a = 10.4749(8), b = 13.4210(9), c = 15.1090(10)Å, β = 103.811(3)° Z = 2; [Cu 4 (obipy) 4 (fum)]·6H 2 O ( 2 ) has the triclinic space group P1¯, with a = 10.1302(11), b = 10.4406(12), c = 11.4450(13)Å, α = 84.384(2)°, β = 79.064(2)°, g = 67.734(2)° and Z = 1. The fumaric acid ligand acts as a multi‐dentate bridging ligand in both compounds, 1 and 2 , to link copper atoms into dumbbell structure. During the reactions, 1, 10‐phenanthroline and 2, 2′‐bipyridine ligands are all hydroxylated into ophen and obipy , which provide useful structural evidence for the study on the Gillard mechanism.