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Interactions of an asymmetric amine with a non-C2 symmetric Cu-salen complex: An EPR/ENDOR and HYSCORE investigation

Caretti, Ignacio, Carter, Emma ORCID:, Fallis, Ian Andrew ORCID:, Murphy, Damien Murphy ORCID: and Van Doorslaer, Sabine 2011. Interactions of an asymmetric amine with a non-C2 symmetric Cu-salen complex: An EPR/ENDOR and HYSCORE investigation. Physical Chemistry Chemical Physics 13 (45) , pp. 20427-20434. 10.1039/c1cp22522g

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Single enantiomers of R-/S-methylbenzylamine (MBA) were found to selectively form adducts with the chiral non-C2 symmetric Cu–salen 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1463-9076
Funders: EPSRC
Last Modified: 03 Dec 2022 11:48

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