Pushing 3c-4e Bonds to the Limit: A Coupled Cluster Study of Stepwise Fluorination of First-Row Atoms

Autor(es)

Oliveira, Vytor P. ^[1] ; Kraka, Elfi ^[2] ; Machado, Francisco B. C. ^[1]

Afiliação do(s) autor(es)

^[1] ITA, Dept Quim, BR-12228900 Sao Jose Dos Campos, SP - Brazil

^[2] Southern Methodist Univ, Dept Chem, 3215 Daniel Ave, Dallas, TX 75275 - USA

• Tipo de documento: Artigo Científico
• Fonte: Inorganic Chemistry; v. 58, n. 21, p. 14777-14789, NOV 4 2019.
• Citações Web of Science: 0

Resumo

To better understand why hypervalent F, O, N, C, and B compounds are rarely stable, we carried out a systematic study of 28 systems, including anionic, cationic, and neutral molecules, held together by covalent, hypervalent, and noncovalent bonds. Molecular geometries, frequencies, atomic charges, electrostatic potentials, energy and electron densities, Mayer bond orders, local stretching force constants, and bond strength orders (BSOs) were derived from high accuracy CCSD(T) calculations and utilized to compare the strength and nature of hypervalent bonds with other types of bonds. All hypervalent molecules studied in this work were found to be either first-order transition states or unstable to dissociation, with F-3(-) and OF3- as the only exceptions. For several systems, we found that a weak noncovalent bonded complex is more stable than a hypervalent one, due to the high energetic cost to accommodate an extra ligand, which can surpass the stability gained by 3c-4e bonding. (AU)

• Processo FAPESP: 18/13673-7 - Desenho de novos reagentes de iodo hipervalente com base em estudos teóricos de elevada acurácia
• Beneficiário: Vytor Pinheiro Oliveira
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 17/07707-3 - Estados excitados e natureza poliradicalar de poliacenos e periacenos
• Beneficiário: Francisco Bolivar Correto Machado
• Modalidade de apoio: Auxílio à Pesquisa - Regular