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Dioxygen Activation Using Schiff Base Macrocyclic Dinuclear Copper( I ) Complexes: Structurally Characterized Dioxygen Reaction Products
Author(s) -
Ma Haiyan,
Allmendinger Markus,
Thewalt Ulf,
Lentz Axel,
Klinga Martti,
Rieger Bernhard
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200211)2002:11<2857::aid-ejic2857>3.0.co;2-#
Subject(s) - chemistry , schiff base , acetonitrile , reactivity (psychology) , diethylenetriamine , ligand (biochemistry) , crystallography , metal , molecule , polymer chemistry , stereochemistry , medicinal chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
Schiff‐base condensation of diethylenetriamine with a series of dialdehydes [isophthalaldehyde ( 2a ), 5‐ tert ‐butylisophthalaldehyde ( 2b ), 2‐methylisophthalaldehyde ( 2c ), and p ‐phthalaldehyde ( 2d )] affords four hexaaza macrocyclic ligands [L H,H ( 3a ), L t Bu,H ( 3b ), L H,Me ( 3c ), L p ‐H,H ( 3d )] bearing different substituents on the aromatic units that connect the two metal ion binding sites. The dinuclear copper( I ) complexes [L H,H Cu 2 (MeCN) 2 ](ClO 4 ) 2 ( 4a ), [L t Bu,H Cu 2 (MeCN) 2 ](ClO 4 ) 2 ( 4b ), [L H,Me Cu 2 (MeCN) 2 ](ClO 4 ) 2 ( 4c ), and [L p −H,H Cu 2 (MeCN) 2 ](CF 3 SO 3 ) 2 ( 4d ) are obtained in good yields by reaction with Cu I salts. X‐ray diffraction studies performed on 4a and 4d reveal a distorted tetrahedral coordination geometry around each Cu I ion, which is constructed by three nitrogen donors of the macrocyclic ligand and one acetonitrile solvent molecule. Treatment of these complexes with molecular dioxygen shows that their reactivity can be fine‐tuned by the nature of the aromatic unit of the dialdehyde building blocks. Thus two different dinuclear Cu II complexes resulting from the reaction of 4a and 4b with dioxygen were isolated and characterized by single crystal X‐ray diffraction, XPS and magnetic measurements. The introduction of a methyl group in the 2‐position of the aromatic spacers in 4c hinders such oxygen transfer reactions but may allow the characterization of stable dioxygen binding species. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)