NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study
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2005
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Conformational analysis based on an analysis of the vicinal alpha- and beta-proton coupling constants of (S)-tyrosinato ligands in diastereomers of a bis[(S)-tyrosinato](1,3-diaminopropane)cobalt(III) complex is used to calculate the mol fractions of the three most stable rotamers (t, g, h) of the (S)-tyrosinato ligand's side groups in D2O solution. The results of this conformational analysis indicate a population increase in the sterically least favorable rotamer h in diastereomers of Cl-molecular symmetry (complexes 5 and 6). The TOCSY spectrum of complex 6 in aqueous solution shows an exceptionally small chemical shift of one NH2 proton from the coordinated diamine, which is explained by an interligand NH center dot center dot center dot pi interaction. These findings demonstrate the persistence of this weak, noncovalent interaction in water solution. DFT calculations for complex 6, whose diamine ring is in a chair conformation, indicate that the complex with an h conformation in bo...th its (S)-tyrosinato ligand side-residues, which yields the most frequent NH center dot center dot center dot pi interactions, represents an energy minimum. The fact that coordinated 1,3-diaminopropane in the examined complex 6 is in a chair conformation in aqueous solution is proved by the NMR analysis. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Ključne reči:
amino acids / cobalt / conformational analysis / density functional calculations / NMR spectroscopy / Pi interactionsIzvor:
European Journal of Inorganic Chemistry, 2005, 15, 3172-3178Izdavač:
- Wiley-V C H Verlag Gmbh, Weinheim
DOI: 10.1002/ejic.200400873
ISSN: 1434-1948
WoS: 000231340900027
Scopus: 2-s2.0-23744467539
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Institucija/grupa
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Miodragović Đenana U. AU - Vitnik, ZJ AU - Milosavljević, Slobodan M. AU - Malinar, M.J. AU - Juranić, Ivan O. PY - 2005 UR - https://cherry.chem.bg.ac.rs/handle/123456789/727 AB - Conformational analysis based on an analysis of the vicinal alpha- and beta-proton coupling constants of (S)-tyrosinato ligands in diastereomers of a bis[(S)-tyrosinato](1,3-diaminopropane)cobalt(III) complex is used to calculate the mol fractions of the three most stable rotamers (t, g, h) of the (S)-tyrosinato ligand's side groups in D2O solution. The results of this conformational analysis indicate a population increase in the sterically least favorable rotamer h in diastereomers of Cl-molecular symmetry (complexes 5 and 6). The TOCSY spectrum of complex 6 in aqueous solution shows an exceptionally small chemical shift of one NH2 proton from the coordinated diamine, which is explained by an interligand NH center dot center dot center dot pi interaction. These findings demonstrate the persistence of this weak, noncovalent interaction in water solution. DFT calculations for complex 6, whose diamine ring is in a chair conformation, indicate that the complex with an h conformation in both its (S)-tyrosinato ligand side-residues, which yields the most frequent NH center dot center dot center dot pi interactions, represents an energy minimum. The fact that coordinated 1,3-diaminopropane in the examined complex 6 is in a chair conformation in aqueous solution is proved by the NMR analysis. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005. PB - Wiley-V C H Verlag Gmbh, Weinheim T2 - European Journal of Inorganic Chemistry T1 - NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study IS - 15 SP - 3172 EP - 3178 DO - 10.1002/ejic.200400873 ER -
@article{ author = "Miodragović Đenana U. and Vitnik, ZJ and Milosavljević, Slobodan M. and Malinar, M.J. and Juranić, Ivan O.", year = "2005", abstract = "Conformational analysis based on an analysis of the vicinal alpha- and beta-proton coupling constants of (S)-tyrosinato ligands in diastereomers of a bis[(S)-tyrosinato](1,3-diaminopropane)cobalt(III) complex is used to calculate the mol fractions of the three most stable rotamers (t, g, h) of the (S)-tyrosinato ligand's side groups in D2O solution. The results of this conformational analysis indicate a population increase in the sterically least favorable rotamer h in diastereomers of Cl-molecular symmetry (complexes 5 and 6). The TOCSY spectrum of complex 6 in aqueous solution shows an exceptionally small chemical shift of one NH2 proton from the coordinated diamine, which is explained by an interligand NH center dot center dot center dot pi interaction. These findings demonstrate the persistence of this weak, noncovalent interaction in water solution. DFT calculations for complex 6, whose diamine ring is in a chair conformation, indicate that the complex with an h conformation in both its (S)-tyrosinato ligand side-residues, which yields the most frequent NH center dot center dot center dot pi interactions, represents an energy minimum. The fact that coordinated 1,3-diaminopropane in the examined complex 6 is in a chair conformation in aqueous solution is proved by the NMR analysis. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.", publisher = "Wiley-V C H Verlag Gmbh, Weinheim", journal = "European Journal of Inorganic Chemistry", title = "NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study", number = "15", pages = "3172-3178", doi = "10.1002/ejic.200400873" }
Miodragović Đenana U., Vitnik, Z., Milosavljević, S. M., Malinar, M.J.,& Juranić, I. O.. (2005). NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study. in European Journal of Inorganic Chemistry Wiley-V C H Verlag Gmbh, Weinheim.(15), 3172-3178. https://doi.org/10.1002/ejic.200400873
Miodragović Đenana U., Vitnik Z, Milosavljević SM, Malinar M, Juranić IO. NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study. in European Journal of Inorganic Chemistry. 2005;(15):3172-3178. doi:10.1002/ejic.200400873 .
Miodragović Đenana U., Vitnik, ZJ, Milosavljević, Slobodan M., Malinar, M.J., Juranić, Ivan O., "NH...pi interactions stabilize the most-hindered rotamer of the (S)-tyrosinato side group in bis[(S)-tyrosinato](diamine)cobalt(III) complexes: An NMR spectroscopic and DFT study" in European Journal of Inorganic Chemistry, no. 15 (2005):3172-3178, https://doi.org/10.1002/ejic.200400873 . .