How computational methods and relativistic effects influence the study of chemical reactions involving Ru‐NO complexes?

Abstract

Two treatments of relativistic effects, namely effective core potentials (ECP) and all-electron scalar relativistic effects (DKH2), are used to obtain geometries and chemical reaction energies for a series of ruthenium complexes in B3LYP/def2-TZVP calculations. Specifically, the reaction energies of reduction (A-F), isomerization (G-I), and Cl negative trans influence in relation to NH (J-L) are considered. The ECP and DKH2 approaches provided geometric parameters close to experimental data and the same ordering for energy changes of reactions A-L. From geometries optimized with ECP, the electronic energies are also determined by means of the same ECP and basis set combined with the computational methods: MP2, M06, BP86, and its derivatives, so as B2PLYP, LC-wPBE, and CCSD(T) (reference method). For reactions A-I, B2PLYP provides the best agreement with CCSD(T) results. Additionally, B3LYP gave the smallest error for the energies of reactions J-L. © 2017 Wiley Periodicals, Inc.

Metal–Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes

“…Results for SAPT0-DKH2 calculations for complexes 1 , 4 , and 7 indicate that the inclusion of these corrections are not significant and do not affect the qualitative interpretation of results (Tables and S1). These observations are in line with a study that compares RECP and DKH2 relativistic approximations, which conclude that the effect of these treatments are similar …”

“…Continuing our interest in ruthenium chemistry, , in this work we investigate whether the gradual increase in the number of bridges, going from [2 2 ]­(1,4)­cyclophane to [2 6 ]­(1,2,3,4,5,6)­cyclophane, superphane, has in fact any direct effect on the nature and magnitude of the cation-π interactions between ruthenium­(II) and [2 n ]-cyclophane ligands. For that reason, the set of complexes [Ru­(η 6 -C n H n )­(NH 3 ) 3 ] 2+ ( n = 16, 18, 20, 22, and 24) ( 1 – 9 ) was studied (Figure ).…”

Impact of substituent nature in diformylpyridyl Schiff base on photophysical and electrochemical properties of ruthenium- and iron-based complexes

“…A similar result was published earlier. [27][28][29][30] Regarding the calculation of the absorption spectrum, we found that previously published results of TD-DFT calculations for Ru-based complexes with a Lanl2DZ basis set comply well with the experimental data. 25 Reference calculations to choose the correct calculation protocol for the simulation of UV-vis spectra for well-known ruthenium-based sensitizer black dye (N719) were performed.…”

How does the pH influences the Ru‐NO coordination compounds?

“…This study continues our investigations into Ru‐NO coordination compounds and advances the analysis of the reactivity of potential NO donors or scavengers fac ‐[Ru(NO)Cl 2 (κ 3 N 4 ,N 8 ,N 11 [1‐carboxypropyl]cyclam)] + , 1 , and its derivatives obtained from a rise in pH, namely 2 from O‐H group deprotonation (pK a = 3.3), 3 from N( 2 )‐H group deprotonation (pK a = 8.0), and 4 from Ru‐NO conversion to Ru‐NO 2 (pK a = 11.5) . Here, we have investigated what the behavior and the nature of the main interactions: (a) Ru‐N(cyclam); (b) Ru‐Cl; (c) N‐H⋯ ·OCO; (d) Ru‐N( 5 )O; (e) Ru‐N( 5 )O 2 ; and (f) N( 5 )‐O, present in the complex fac ‐[Ru(NO)Cl 2 (κ 3 N 4 ,N 8 ,N 11 [1‐carboxypropyl]cyclam)] + , 1 , and in its derivatives, 2 ‐ 4 , through the pH variation (Scheme ).…”