Title
Interactions of an asymmetric amine with a <tex>$non-C_{2}$</tex> symmetric Cusalen complex : an EPR/ENDOR and HYSCORE investigation Interactions of an asymmetric amine with a <tex>$non-C_{2}$</tex> symmetric Cusalen complex : an EPR/ENDOR and HYSCORE investigation
Author
Faculty/Department
Faculty of Sciences. Physics
Publication type
article
Publication
Cambridge ,
Subject
Physics
Chemistry
Source (journal)
Physical chemistry, chemical physics / Chemical Society [London] - Cambridge, 1999, currens
Volume/pages
13(2011) :45 , p. 20427-20434
ISSN
1463-9076
1463-9084
ISI
000296871500049
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
Single enantiomers of R-/S-methylbenzylamine (MBA) were found to selectively form adducts with the chiral non-C2 symmetric Cusalen complex N-(3,5-di-tert-butylsalicylidene)-N′-(salicylidene)-cyclohexane-1,2-diamine copper(II), hereafter labelled [Cu(3)]. The g/A spin Hamiltonian parameters of this Cu(II) complex showed a decrease in symmetry from axial to rhombic upon formation of the [Cu(3)] + MBA adducts. The selectivity in enantiomeric discrimination was found to be only 59 ± 5% in favour of the heterochiral R,R′-[Cu(3)] + S-MBA and S,S′-[Cu(3)] + R-MBA adducts. This was directly evidenced by W-band EPR spectroscopy. The observed low selectivity for enantiomer discrimination is primarily attributed to the loss of the bulky tert-butyl groups from the 3,5 positions of [Cu(3)] compared to the parent N,N′-bis(3,5-di-tert-butylsalicylidene)-cyclohexane-1,2-diamine copper(II) ligand (labelled [Cu(1)]). The structure of the [Cu(3)] complex in the presence and absence of coordinating amine was further investigated by analysis of the ligand hyperfine interactions, as revealed through Q-band CW-ENDOR, X-band Davies ENDOR and HYSCORE. 1H couplings from the NH2 group of the amine, observed by ENDOR and HYSCORE, provided direct evidence of amine coordination.
E-info
https://repository.uantwerpen.be/docman/iruaauth/061951/7045fc27841.pdf
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