Unveiling the electronic and molecular structure of a trinuclear ruthenium cluster containing one nitrosyl ligand

Author(s)

Batista, Ana Paula de Lima ; Pavan, Jamile Rocha ; Ribeiro, Marcos Antonio ; Nikolaou, Sofia

• Document type: Journal article
• Source: Journal of Molecular Structure; v. 1308, p. 10-pg., 2024-03-29.

Abstract

The understanding of the Ru-NO bond in Ru nitrosyl systems is of great interest due to the non-innocent nature of the NO ligand, and because of the ability of such compounds to release nitric oxide, an essential physiological regulator. The Ru-NO bond description can be even more complicated when it comes to polynuclear systems such as the mu-oxo clusters of general formula [Ru3O(CH3COO)6(L)3]n, which can be electronically localized or delocalized themselves depending on the nature of the L ligands, or present unpaired electrons depending on the Ru ions oxidation state. Herein, we present a detailed electronic- and molecular-structure description of the [Ru3O (CH3COO)6(py)2NO]PF6 (py = pyridine) cluster using multiconfigurational approaches and X-ray diffraction analysis. The X-ray data unveil a linear Ru-NO moiety with a Ru-NO angle of 180 degrees. Although most linear {RuNO}6 complexes have been largely described as RuII-NO+, our valence bond-type analysis based on a CASSCF ground state wavefunction, with an active space comprised of 18 electrons and 16 orbitals, showed a predominance of the RuIII-NO degrees configuration, with minor contributions from RuIV-NO- and RuII-NO+. These findings provide a more precise framework to rationalize the electronic properties of trinuclear ruthenium nitrosyls, aiding the planning of new NO releasers based on those clusters. (AU)

• FAPESP's process: 22/03478-8 - Reactivity of polynuclear ruthenium compounds with potential biological application
• Grantee: Sofia Nikolaou
• Support Opportunities: Regular Research Grants
• FAPESP's process: 18/18060-3 - Use of inorganic supramolecular structures for the development of functional molecules and controlled release of bioactive species
• Grantee: Sofia Nikolaou
• Support Opportunities: Regular Research Grants
• FAPESP's process: 22/12043-5 - Structure and spectroscopy of first row transition metal complexes: a computacional approach
• Grantee: Ana Paula de Lima Batista
• Support Opportunities: Regular Research Grants
• FAPESP's process: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis
• Grantee: Roberto Manuel Torresi
• Support Opportunities: Research Projects - Thematic Grants