Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 21st October 2020 from 07:00 AM to 07:00 PM (BST).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.

Issue 27, 2020
Previous Article Next Article

Tracking the role of trans-ligands in ruthenium–NO bond lability: computational insight

Author affiliations


Nitric oxide (NO) is an important endogenously produced molecule. Ruthenium–NO tetraamine complexes appear as model structures to investigate the control of nitric oxide bioavailability. NO release typically occurs through the trans-[RuII(NH3)4Ltrans(NO+)]3+/2+ + etrans-[RuII(NH3)4Ltrans(NO0)]2+/+ reduction reaction, followed by the trans-[RuII(NH3)4Ltrans(NO0)]2+/+ + H2O → trans-[RuII(NH3)4Ltrans(H2O)]2+/+ + NO0 hydrolysis reaction. The choice of the NO trans ligand, Ltrans, is fundamental to control the Ru–NO bond stability. Here, the nature and charge influences of Ltrans were evaluated considering the following ligands Ltrans = σ-donors (NH3 and H), π-donors (H2O and NH2), and π-donors and π-acceptors (CO and CN) through the ZORA-BP86/TZ2P computational model. Energy Decomposition Analysis in conjunction with the Natural Orbitals for Chemical Valence methodology (EDA-NOCV) showed that molecules with Ltrans = H2O and NH2 promoted larger Ru–NO stabilization than complexes with Ltrans = NH3 and H, respectively, mainly due to the interaction orbital energy (ΔEoi). The opposite trend was observed in compounds with Ltrans = CO and CN compared to structures with Ltrans = H2O and NH2. The study of the charge distribution, performed using the Voronoi Deformation Density (VDD) method, and the topological analysis of the electron density, realized using the Quantum Theory of Atoms in Molecules (QTAIM), on the investigated complexes indicated that Ltrans with negative charge promoted, in general, predominantly a decrease of the electron flux in the Ltrans(σ) → Ru(dσ*) ← NO(σ) process.

Graphical abstract: Tracking the role of trans-ligands in ruthenium–NO bond lability: computational insight

Back to tab navigation

Supplementary files

Article information

17 Mar 2020
14 Jun 2020
First published
15 Jun 2020

New J. Chem., 2020,44, 11448-11456
Article type

Tracking the role of trans-ligands in ruthenium–NO bond lability: computational insight

R. P. Orenha, G. C. G. Silva, A. P. de Lima Batista, A. G. S. de Oliveira Filho, N. H. Morgon, V. B. da Silva, S. S. P. Furtado, G. F. Caramori, M. J. Piotrowski and R. L. T. Parreira, New J. Chem., 2020, 44, 11448
DOI: 10.1039/D0NJ01340D

Social activity

Search articles by author