How to tune the Ru-NO coordination bond: insight from Kohn-Sham molecular orbital theory and energy decomposition analyses

• Grant number: 15/15176-2
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• Start date: October 30, 2015
• End date: October 29, 2016
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Sergio Emanuel Galembeck
• Grantee: Renato Pereira Orenha
• Supervisor: Frederick Matthias Bickelhaupt
• Host Institution: Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto (FFCLRP). Universidade de São Paulo (USP). Ribeirão Preto , SP, Brazil
• Institution abroad: University Amsterdam (VU), Netherlands
• Associated to the scholarship: 11/20351-7 - Computational study of ruthenium-nitosyl compounds, BP.DD

Abstract

The biological relevance of nitric oxide has triggered an enormous interest in the physicochemical properties of these molecules and many experimental and theoretical studies have been devoted to explore its behavior and involvement in biochemical processes. An issue of great importance is the controlled release of NO into, or its removal from a physiological environment using in particular ruthenium complexes which are stable in aqueous solution towards air oxidation. Interestingly, the Ru-NO bonding mechanism in the [RuNO]n core, which is key to the desired steering of NO release or uptake, is still poorly understood. In this project, we tackle this problem through sophisticated bonding analyses in a series of model complexes using relativistic Kohn-Sham density functional theory at ZORA-BP86/TZ2P. Thus, we will explore and analyze cis-[RuCl(NO)(NH3)4]2+, 1, cis-[RuCl(NO)(NH3)4]1+, 2, trans-[RuCl(NO)(NH3)4]2+, 3, trans-[RuCl(NO)(NH3)4Cl]1+, 4, [Ru(NO)(NH3)5]3+, 5, [Ru(NO)(NH3)5]2+, 6, besides fac-[Ru(NO)Cl2(º3N4,N8,N11(1-carboxypropyl)cyclam)]Cl·H2O, 7, and its derivatives from deprotonation of the carboxyl, 8, and the N-H group, 9. The Kohn-Sham MO bonding mechanism of the Ru-NO bond is to be quantitatively supported by energy decomposition analyses (EDA) and Voronoi Deformation Density (VDD) analyses of the electron density in the various model complexes. (AU)

Scientific publications

(10)

(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)

ORENHA, RENATO P.; CARAMORI, GIOVANNI F.; MISTURINI, ALECHANIA; GALEMBECK, SERGIO E.. Shedding light on the electronic structure of [Ru((6)-C16H16)(NH3)(3)](2+) complex: a computational insight. Journal of Molecular Modeling, v. 25, n. 1, JAN 2019. (15/15176-2, 11/20351-7, 08/02677-0)

ORENHA, RENATO PEREIRA; TFOUNI, ELIA; GALEMBECK, SERGIO EMANUEL. How does the total charge and isomerism influence the Ru-NO ammine complexes?. Physical Chemistry Chemical Physics, v. 20, n. 19, p. 13348-13356, MAY 21 2018. (11/20351-7, 08/02677-0, 15/15176-2, 06/53266-4, 14/50265-3)

ORENHA, RENATO P.; GREGORIO, LETICIA R. SAN; GALEMBECK, SERGIO E.. Computational study of the interaction between NO, NO+, and NO- with H2O. Journal of Molecular Modeling, v. 22, n. 11, NOV 2016. (15/15176-2, 11/20351-7, 14/50265-3, 08/02677-0)

ORENHA, RENATO PEREIRA; SANTIAGO, REGIS TADEU; ANDRADE HAIDUKE, ROBERTO LUIZ; GALEMBECK, SERGIO EMANUEL. How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?. Journal of Computational Chemistry, v. 38, n. 12, p. 883-891, MAY 2017. (15/15176-2, 14/23714-1, 10/18743-1, 11/20351-7, 08/02677-0)

ORENHA, RENATO P.; VESSECCHI, RICARDO; GALEMBECK, SERGIO E.. The influence of the negative hyperconjugation is relevant for the analysis of the pi-pi{*} conjugation with the mono-substitution and di-substitution of H2C= by O= and/or HN= in trans-buta-1,3-diene?. STRUCTURAL CHEMISTRY, v. 29, n. 3, p. 847-857, JUN 2018. (11/20351-7, 14/23604-1, 08/02677-0, 15/15176-2, 09/08712-4, 14/50265-3)

ORENHA, RENATO P.; GALEMBECK, SERGIO E.. How does the pH influences the Ru-NO coordination compounds?. International Journal of Quantum Chemistry, v. 119, n. 20, OCT 15 2019. (14/50265-3, 15/15176-2, 11/20351-7, 08/02677-0)

GALEMBECK, SERGIO E.; CARAMORI, GIOVANNI F.; MISTURINI, ALECHANIA; GARCIA, LEONE C.; ORENHA, RENATO P.. Metal-Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes. Organometallics, v. 36, n. 18, p. 3465-3470, SEP 25 2017. (15/15176-2, 11/20351-7, 14/50265-3, 08/02677-0)

ORENHA, RENATO P.; ROCHA, MARCUS V. J.; POATER, JORDI; GALEMBECK, SERGIO E.; BICKELHAUPT, F. MATTHIAS. Nature of the Ru-NO Coordination Bond: Kohn-Sham Molecular Orbital and Energy Decomposition Analysis. CHEMISTRYOPEN, v. 6, n. 3, p. 410-416, JUN 2017. (15/15176-2, 11/20351-7, 14/50265-3, 08/02677-0)

ORENHA, RENATO P.; VESSECCHI, RICARDO; GALEMBECK, SERGIO E.. The influence of the negative hyperconjugation is relevant for the analysis of the pi-pi* conjugation with the mono-substitution and di-substitution of H2C= by O= and/or HN= in trans-buta-1,3-diene?. STRUCTURAL CHEMISTRY, v. 29, n. 3, p. 11-pg., 2018-06-01. (08/02677-0, 09/08712-4, 14/50265-3, 15/15176-2, 14/23604-1, 11/20351-7)

ORENHA, RENATO PEREIRA; SANTIAGO, REGIS TADEU; ANDRADE HAIDUKE, ROBERTO LUIZ; GALEMBECK, SERGIO EMANUEL. How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?. Journal of Computational Chemistry, v. 38, n. 12, p. 9-pg., 2017-05-01. (08/02677-0, 10/18743-1, 15/15176-2, 14/23714-1, 11/20351-7)