Syntheses, characterization, and reactivity of copper complexes with tridentate N-donor ligands

• Published in: Inorganica Chimica Acta Vol. 361; no. 1; pp. 279 - 292
• Main Authors: Astner, Jörg, Weitzer, Markus, Foxon, Simon P., Schindler, Siegfried, Heinemann, Frank W., Mukherjee, Jhumpa, Gupta, Rajeev, Mahadevan, Viswanath, Mukherjee, Rabindranath
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 2008
• Subjects: Bis-oxo-dicopper(III) species; Copper complexes; Kinetics; Reactivity with dioxygen; Tridentate N-donor ligands; Tridentate N-donor ligands; Bis-oxo-dicopper(III) species; Kinetics; Reactivity with dioxygen; Copper complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2007.07.018

Copper complexes of the tridendate ligands Me
5dien, Et
5dien, Me-bpa and MeL have been investigated. The kinetics for the formation of the dinuclear bis(μ-oxo) copper complex using Me
5dien as a ligand was analyzed using low-temperature stopped-flow instrumentation. Crystal structures for the copper(II) complexes of Me-bpa and MeL are reported.
The reaction of dioxygen with the copper(I) complex of the tridentate ligand 1,1,4,7,7-pentamethyldiethylenetriamine (Me
5dien) has been investigated using low-temperature stopped-flow techniques. The formation of a bis(μ-oxo)copper(III) complex as a reactive intermediate could be detected spectroscopically at low temperatures and a quantitative kinetic analysis was performed for this system. Crystal structures of the copper(II) complexes [(Me-bpa)Cu(Cl)
2] (
1), [{(Me-bpa)Cu(Cl)(ClO
4)}
2] (
2), [{(MeL)Cu(Cl)(ClO
4)}
2] (
3), and [(MeL)Cu(NCS)
2] (
4) (Me-bpa
=
N-methyl-[bis(2-pyridyl)methyl]amine; MeL
=
N-methyl-[(2-pyridyl)ethyl(2-pyridyl)methyl]amine) are reported.