Design of novel hypervalent iodine reagents based on high accuracy theoretical studies

• Grant number: 18/13673-7
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: November 01, 2018
• End date: October 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Francisco Bolivar Correto Machado
• Grantee: Vytor Pinheiro Oliveira
• Host Institution: Divisão de Ciências Fundamentais (IEF). Instituto Tecnológico de Aeronáutica (ITA). Ministério da Defesa (Brasil). São José dos Campos , SP, Brazil

Abstract

Hypervalent iodine compounds have received increased attention from the scientific community because of their versatility as oxidizers and, more recently, as reagents for group transfer reactions of small functional groups such as trifluoromethyl and ethynyl. Hypervalent iodine has reactivity and selectivity comparable to those of the transition metals with the advantage of being less toxic, cheaper, and easier to acquire. Despite these advantages, there still are a few mechanistic studies and limited investigations that attempt to elucidate the relationship between the electronic structure of the reagents and their reactivity. Therefore, the present project aims to conduct a detailed study of the electronic structure and reaction mechanism of hypervalent iodine compounds using innovative computational tools. These tools include: i) local vibrational modes - capable of providing the intrinsic strength of a chemical bond, and ii) the Unified Reaction Valley Approach (URVA) - capable of elucidating the major changes occurring in the electronic structure of the reactants during the many phases of a chemical reaction and the energetic cost associated with these phases. At the end of this project, a new parameter to predict the reactivity of hypervalent compounds will be proposed and novel hypervalent reagents will be suggested. Thus, we expect this project to have a great impact on the development of better and more versatile hypervalent iodine reagents.

Scientific publications

(6)

(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)

OLIVEIRA, VYTOR PINHEIRO; MARCIAL, BRUNA LUANA; MACHADO, FRANCISCO B. C.; KRAKA, ELFI. Relating Bond Strength and Nature to the Thermodynamic Stability of Hypervalent Togni-Type Iodine Compounds. CHEMPLUSCHEM, v. 86, n. 8, p. 1199-1210, AUG 2021. (19/25105-6, 18/13673-7)

FREINDORF, MAREK; YANNACONE, SETH; OLIVEIRA, VYTOR; VERMA, NIRAJ; KRAKA, ELFI. alogen Bonding Involving I-2 and d(8) Transition-Metal Pincer Complexe. CRYSTALS, v. 11, n. 4, APR 2021. (18/13673-7)

OLIVEIRA, VYTOR P.; KRAKA, ELFI; MACHADO, FRANCISCO B. C.. Pushing 3c-4e Bonds to the Limit: A Coupled Cluster Study of Stepwise Fluorination of First-Row Atoms. Inorganic Chemistry, v. 58, n. 21, p. 14777-14789, NOV 4 2019. (18/13673-7, 17/07707-3)

NIEMAN, REED; OLIVEIRA, VYTOR P.; JAYEE, BHUMIKA; AQUINO, ADELIA. J. A.; MACHADO, FRANCISCO B. C.; LISCHKA, HANS. High-Level Multireference Investigations on the Electronic States in Single-Vacancy (SV) Graphene Defects Using a Pyrene-SV Model. Journal of Physical Chemistry A, v. 127, n. 40, p. 10-pg., 2023-10-03. (18/13673-7, 22/16385-8)

ANN DELGADO, ALEXIS ANTOINETTE; SETHIO, DANIEL; MATTHEWS, DEVIN; OLIVEIRA, VYTOR; KRAKA, ELFI. Substituted hydrocarbon: a CCSD(T) and local vibrational mode investigation. Molecular Physics, v. 119, n. 21-22, SI, AUG 2021. (18/13673-7)

OLIVEIRA, VYTOR P.; MARCIAL, BRUNA L.; MACHADO, FRANCISCO B. C.; KRAKA, ELFI. Metal-Halogen Bonding Seen through the Eyes of Vibrational Spectroscopy. MATERIALS, v. 13, n. 1, JAN 1 2020. (18/13673-7)