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 Opportunities: Scholarships abroad - Research
• Start date: February 01, 2015
• End date: January 31, 2016
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Lucas Colucci Ducati
• Grantee: Lucas Colucci Ducati
• Host Investigator: Jochen Autschbach
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Institution abroad: 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)

(The scientific publications listed on this page originate from the Web of Science or SciELO databases. Their authors have cited FAPESP grant or fellowship project numbers awarded to Principal Investigators or Fellowship Recipients, whether or not they are among the authors. This information is collected automatically and retrieved directly from those bibliometric databases.)

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. (14/21930-9)

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. (15/08541-6, 15/11769-9, 15/08539-1, 14/21930-9, 14/15962-5)

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. (11/17357-3, 14/21930-9, 12/12414-1, 17/20890-1, 15/20106-3, 15/08541-6, 17/17750-3, 13/03477-2)

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. (11/17357-3, 13/03477-2, 12/12414-1, 10/15765-4, 14/21930-9)

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. (14/21930-9, 15/08541-6)

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. (11/17357-3, 13/03477-2, 12/12414-1, 15/20106-3, 15/08541-6, 14/21930-9)

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. (14/21930-9)

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. (14/21930-9)

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. (11/17357-3, 13/03477-2, 12/12414-1, 15/20106-3, 15/08541-6, 14/21930-9)

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. (14/21930-9)

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. (14/21930-9)