Ruthenium nitrosyl complexes containing pyridine-functionalized carbenes - A theoretical insight

Author(s)

Caramori, Giovanni F. ^[1] ; Ortolan, Alexandre O. ^[1] ; Parreira, Renato L. T. ^[2] ; da Silva, Eder H. ^[2]

Affiliation

^[1] Univ Fed Santa Catarina, Dept Quim, BR-88040900 Florianopolis, SC - Brazil

^[2] Univ Franca, Nucleo Pesquisa Ciencias Exatas & Tecnol, BR-14404600 Franca, SP - Brazil

• Document type: Journal article
• Source: JOURNAL OF ORGANOMETALLIC CHEMISTRY; v. 799-800, p. 54-60, DEC 15 2015.
• Web of Science Citations: 3

Abstract

The Ru NO bonding situation in a set of ruthenium(II) nitrosyl complexes containing pyridinefunctionalized carbenes as bidentate ligands is presented. Cheng's complex {[}(L)Ru(NO)Cl-3], where L = 3-tert-butyl-1-(2-pyridyl)imidazol-2-ylidene, la, was used as a model structure and the effect of different families of pyridine-functionalized carbene ligands on the Ru NO bond strength was explored, including imidazolylidenes, triazolylidenes, oxazolylidenes, thiazolylidenes, P-heterocyclic carbenes, imidazolidinone, triazolidinone, among others. The results reveal that the NO group binds more strongly to the Ru(II), than carbene carbon or pyridine nitrogen atoms. The EDA-NOCV results show that the nature of the carbene has a direct influence on the lability of the Ru NO, since it changes the electronic environment around the metallic centre. EDA-NOCV results point out that the nature of the Ru NO interactions (1a-16b) presents a very preponderant covalent character (circa 70%), while the electrostatic character covers circa 30% of the total interaction energy. The energy decomposition still reveals that Ru-NO+ bonds are strengthen in complexes la-16a, than in lb-16c. The weakest Ru NO interactions are observed for complexes containing P-heterocyclic ligands (PHCs), specially for complexes where the NO is coordinated trans to the carbene carbon atoms. The metal, ligand r-back-donation is more intense towards PHC than towards NO+. (C) 2015 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion
• Grantee: Renato Luis Tame Parreira
• Support Opportunities: Research Grants - Young Investigators Grants