title: Syntheses and characterization of two dioxygen-reactive dinuclear macrocyclic schiff-base copper(I) complexes.
abstract: The dinuclear copper(I) complex [Cu(2)L(1)(CH(3)CN)(2)](ClO(4))(2) (1, L(1) = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 with dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L(1) could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.
authors.affiliation: Institut für Anorganische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, Germany.
authors.forename: Diana
authors.initials: D
authors.lastname: Utz
authors.forename: Frank W
authors.initials: FW
authors.lastname: Heinemann
authors.forename: Frank
authors.initials: F
authors.lastname: Hampel
authors.forename: David T
authors.initials: DT
authors.lastname: Richens
authors.forename: Siegfried
authors.initials: S
authors.lastname: Schindler