Preparation of the copper(II) complex of the binucleating hexaaza macrocycle 2,5,8,17,20,23-hexaaza[9.9]paracyclophane and its solution chemistry, hydrolytic activity and acid dissociation kineticsâ â Electronic supplementary information (ESI) available: 2-D NOESY NMR spectra, experimental details of the potentiometric, spectrophotometric and crystallographic studies. See http://www.rsc.org/suppdata/dt/b0/b006199i/
Clifford, Thomas; Danby, Andrew M.; Lightfoot, Philip; Richens, David T.; Hay, Robert W.; Clifford Thomas; Department of Chemistry, University of Kansas, Malott Hall; Danby Andrew M.; Department of Chemistry, University of Kansas, Malott Hall; Lightfoot Philip; School of Chemistry, University of St. Andrews; Richens David T.; School of Chemistry, University of St. Andrews; Hay Robert W.; School of Chemistry, University of St. Andrews
Журнал:
Dalton Transactions
Дата:
2001
Аннотация:
The binucleating hexaaza macrocycle 2,5,8,17,20,23-hexaaza[9.9]paracyclophane (PEA) and its N-permethylated derivative 2,5,8,17,20,23-hexamethyl-2,5,8,17,20,23-hexaaza[9.9]paracyclophane (Me6PEA) have been prepared. The copper(II) complex of PEA has been prepared and the stability constants of the copper complexes determined in aqueous solution by potentiometric and spectrophotometric methods. The protonation sites of PEA have been identified by NMR titration. The crystal structure of the complex [Cu2(PEA)Cl3]<sup>+</sup>Cl<sup>â </sup>·2.6MeCN·2.9H2O has been determined. The copper centres have an N3Cl2 donor set with a square pyramidal geometry. The Cuâ â ¯â Cu distance is 7.02 à . The copper complex catalyses hydrolysis of the phosphotriester 2,4-dinitrophenyl diethyl phosphate (DNPDEP) and the [Cu2(PEA)(OH)2]<sup>2+</sup> and [Cu2(PEA)(OH)]<sup>3+</sup> complexes have been identified as the active species. The acid catalysed dissociation of the copper complex has been studied by stopped-flow methods. The reaction is monophasic and displays saturation kinetics at high acidities.
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