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Titolo:
Coordination chemistry of unsymmetrical tripodal ligands with an NNO2 donor set
Autore:
Ochs, C; Hahn, FE; Frohlich, R;
Indirizzi:
Free Univ Berlin, Inst Anorgan & Analyt Chem, D-14195 Berlin, Germany FreeUniv Berlin Berlin Germany D-14195 yt Chem, D-14195 Berlin, Germany Univ Munster, Inst Anorgan Chem, D-48149 Munster, Germany Univ Munster Munster Germany D-48149 rgan Chem, D-48149 Munster, Germany Univ Munster, Inst Organ Chem, D-48149 Munster, Germany Univ Munster Munster Germany D-48149 rgan Chem, D-48149 Munster, Germany
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 9, , anno: 2001,
pagine: 2427 - 2436
SICI:
1434-1948(200109):9<2427:CCOUTL>2.0.ZU;2-0
Fonte:
ISI
Lingua:
ENG
Soggetto:
GALACTOSE-OXIDASE; ACTIVE-SITE; COPPER(II) COMPLEXES; CRYSTAL-STRUCTURE; AEROBIC OXIDATION; TC-99M COMPLEXES; MEDICAL INTEREST; MODELS; FORM; TETRAAMINES;
Keywords:
tripodal ligands; copper; radicals; N ligands; O ligands;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
49
Recensione:
Indirizzi per estratti:
Indirizzo: Hahn, FE Free Univ Berlin, Inst Anorgan & Analyt Chem, Fabeckstr 34-36, D-14195 Berlin, Germany Free Univ Berlin Fabeckstr 34-36 Berlin Germany D-14195 Germany
Citazione:
C. Ochs et al., "Coordination chemistry of unsymmetrical tripodal ligands with an NNO2 donor set", EUR J INORG, (9), 2001, pp. 2427-2436

Abstract

The synthesis of two new tripodal ligands N(CH2CH2NH2)(CH2CH2CH2OH)(2) (H-4-1) and N[2,3,5-C6H2(OH)(SCH3)(CH3)](CH2CH2CH2NH2)(CH2CH2CH2OH) (H4-2) is reported. Both tetradentate ligands contain a central tertiary nitrogen atom, as well as two OH and one NH2 functionalized ligand arm. The tripods do not only exhibit an unsymmetrical N2O2 donor set, but also possess two C-3 and one C-2 chains between the central nitrogen atom and the terminal donors. On coordination of the central tertiary nitrogen atom, the ligands are capable of forming both six- and five-membered chelate rings in their metal complexes. Both ligands react with [Cu(OAc)(2).H2O](2) to give the dinuclear copper(II) complexes [Cu(eta (4)-mu -O-H-3-1)(2)Cu](PF6)(2) (3) and [(etaH-3(3)-2)Cu( mu -OAc)(2)Cu(eta (3)-H-3-2)]. 2CH(3)CN (4 . 2CH(3)CN). The molecular structures of 3 and 4.2CH3CN have been determined by X-ray diffraction. Complex 3 contains two slightly distorted square-pyramidal (tau = 0.181) copper atoms, with O-donors in the apical positions. The dinuclear complex 4, which was synthesized to model the copper site in galactose oxidase,also shows a distorted square-pyramidal coordination geometry (tau = 0.205and tau = 0.101) around both copper(II) atoms. Complex 4 contains two uncoordinated primary alcohol functionalities of the ligands. In addition, boththe ligand H-4-2 and its dinuclear copper complex [(eta (3)-H-3-2)Cu(mu -OAc)(2)(eta (3)-H-3-2)]. 2CH(3)CN can easily be oxidized to yield free or coordinated phenoxyl radicals, which are stable on the time scale of cyclic voltammetry.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 05/04/20 alle ore 23:55:00