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Study of the solvent effect on the spin spin coupling constant 1JPt-Tl in heavy metal complexes by ab initio molecular dynamics

Grant number: 14/21930-9
Support type:Scholarships abroad - Research
Effective date (Start): February 01, 2015
Effective date (End): January 31, 2016
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal Investigator:Lucas Colucci Ducati
Grantee:Lucas Colucci Ducati
Host: Jochen Autschbach
Home Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Local de pesquisa : State University of New York, Buffalo State (SUNY), United States  

Abstract

This project aims to study the solvent effect influence on the 1JPt-Tl spin-spin coupling constant in metal complexes that exhibit a metal-metal bond between Pt and Tl. These 1JPt-Tl spin-spin coupling constants have a strong solvent effect influence. Previous works showed that the calculated values of 1JTlPt for isolated complexes reproduce about 50% of the experimental value, while the same NMR calculation for the complexes in the presence of some solvent molecules can describe about 80% of the experimental 1JPt-Tl value.In this project the inclusion of solvent effect by ab inito molecular dynamics (aiMD) in the calculation of the coupling constant 1JTlPt is proposed. This new approach to the description of the effect of the solvent in the calculation of magnetic properties at the DFT-ZORA level has been successfully applied to cisplatin complexes, obtaining an accuracy of approximately 95%.To explain the reason for the strong influence of the solvent effect on the studied coupling constant, the 1JTlPt values will be decomposed into contributions from bonding, non-bonding, core, and antibonding orbitals applying the "Analysis of Natural Coupling Constant" (NJC), which provides an interpretation of the results with a chemical sense. Another issue to be studied is the nature of the complexes' Pt-Tl chemical bond using the energy decomposition analysis (EDA) method. This will allow assessing the change in electron density across the Pt-Tl bond, when the complex is solvated, supplementing NJC results, since the Pt-Tl bond is the transmission path for the coupling constant between these two metal centers. (AU)

Scientific publications (11)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
VIESSER, RENAN V.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.; AUTSCHBACH, JOCHEN. The halogen effect on the C-13 NMR chemical shift in substituted benzenes. Physical Chemistry Chemical Physics, v. 20, n. 16, p. 11247-11259, APR 28 2018. Web of Science Citations: 9.
SURBELLA, III, ROBERT G.; DUCATI, LUCAS C.; AUTSCHBACH, JOCHEN; DEIFEL, NICHOLAS P.; CAHILL, CHRISTOPHER L. Thermochromic Uranyl Isothiocyanates: Influencing Charge Transfer Bands with Supramolecular Structure. Inorganic Chemistry, v. 57, n. 5, p. 2455-2471, MAR 5 2018. Web of Science Citations: 10.
CARTER, KOREY P.; KALAJ, MARK; SURBELLA, III, ROBERT G.; DUCATI, LUCAS C.; AUTSCHBACH, JOCHEN; CAHILL, CHRISTOPHER L. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms. CHEMISTRY-A EUROPEAN JOURNAL, v. 23, n. 61, p. 15355-15369, NOV 2 2017. Web of Science Citations: 17.
SURBELLA, III, ROBERT G.; DUCATI, LUCAS C.; PELLEGRINI, KRISTI L.; MCNAMARA, BRUCE K.; AUTSCHBACH, JOCHEN; SCHWANTES, JON M.; CAHILL, CHRISTOPHER L. A new Pu(III) coordination geometry in (C5H5NBr)(2)[PuCl3(H2O)(5)].2Cl.2H(2)O as obtained via supramolecular assembly in aqueous, high chloride media. CHEMICAL COMMUNICATIONS, v. 53, n. 78, p. 10816-10819, OCT 7 2017. Web of Science Citations: 2.
CORRERA, THIAGO CARITA; FERNANDES, ANDRE SANTOS; REGINATO, MARCELO MOTA; DUCATI, LUCAS COLUCCI; BERDEN, GIEL; OOMENS, JOS. Probing the geometry reorganization from solution to gas-phase in putrescine derivatives by IRMPD, H-1-NMR and theoretical calculations. Physical Chemistry Chemical Physics, v. 19, n. 35, p. 24330-24340, SEP 21 2017. Web of Science Citations: 4.
VIESSER, RENAN V.; DUCATI, LUCAS C.; TORMENA, CLAUDIO F.; AUTSCHBACH, JOCHEN. The unexpected roles of sigma and pi orbitals in electron donor and acceptor group effects on the C-13 NMR chemical shifts in substituted benzenest. CHEMICAL SCIENCE, v. 8, n. 9, p. 6570-6576, SEP 2017. Web of Science Citations: 13.
SURBELLA, III, ROBERT G.; DUCATI, LUCAS C.; PELLEGRINI, KRISTI L.; MCNAMARA, BRUCE K.; AUTSCHBACH, JOCHEN; SCHWANTES, JON M.; CAHILL, CHRISTOPHER L. Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly. Journal of the American Chemical Society, v. 139, n. 31, p. 10843-10855, AUG 9 2017. Web of Science Citations: 17.
DUCATI, LUCAS C.; MARCHENKO, ALEX; AUTSCHBACH, JOCHEN. NMR J-Coupling Constants of TI-Pt Bonded Metal Complexes in Aqueous Solution: Ab Initio Molecular Dynamics and Localized Orbital Analysis. Inorganic Chemistry, v. 55, n. 22, p. 12011-12023, NOV 21 2016. Web of Science Citations: 3.
ABDULLAYEV, YUSIF; ABBASOV, VAGIF; DUCATI, LUCAS C.; TALYBOV, AVTANDIL; AUTSCHBACH, JOCHEN. Ionic Liquid Solvation versus Catalysis: Computational Insight from a Multisubstituted Imidazole Synthesis in [Et2NH2][HSO4]. CHEMISTRYOPEN, v. 5, n. 5, p. 460-469, OCT 2016. Web of Science Citations: 2.
VIESSER, RENAN V.; DUCATI, LUCAS C.; AUTSCHBACH, JOCHEN; TORMENA, CLAUDIO F. NMR spin-spin coupling constants: bond angle dependence of the sign and magnitude of the vicinal (3)J(HF) coupling. Physical Chemistry Chemical Physics, v. 18, n. 34, p. 24119-24128, SEP 14 2016. Web of Science Citations: 4.
VIESSER, RENAN V.; DUCATI, LUCAS C.; AUTSCHBACH, JOCHEN; TORMENA, CLAUDIO F. Effects of stereoelectronic interactions on the relativistic spin-orbit and paramagnetic components of the C-13 NMR shielding tensors of dihaloethenes. Physical Chemistry Chemical Physics, v. 17, n. 29, p. 19315-19324, 2015. Web of Science Citations: 8.

Please report errors in scientific publications list by writing to: cdi@fapesp.br.