The Effect of trans Ligands in the NO‐Linkage Reverse Isomerization for Ruthenium–Nitrosyl–Tetraammine Complexes: A DFT Study

Abstract

The rearrangement of the NO ligand in rutheniumnitrosyl-tetraammine complexes trans-[Ru(NO)(NH 3 ) 4 X] 2+ (X = F -, Cl -, OH -, SH -) has been studied for metastable oxygen-coordinated NO complexes by means of DFT. On the basis of obtained data, this rearrangement is concluded to be caused by [a] Nikolaev

Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes

“…The T d values for MS1 and MS2 are 292 and 206 K, respectively. The T d for MS1 in trans-[RuNO(NH 3 ) 4 F]SiF 6 is the highest decay temperature known up to now (see Table 3), thereby confirming that the fluorine ligand trans to NO has a positive effect on the thermal stability (Yamaletdinov & Zilberberg, 2017;Kostin et al, 2018). In order to illustrate the influence of the trans-to-NO ligand on the thermal stability of MS1, Table 3 summarizes the kinetic parameters of the MS1!GS reaction for a series of complexes with the same ligand environment (NH 3 , ethylenediamine and pyridine in the equatorial position) and charge.…”

“…In order to illustrate the influence of the trans-to-NO ligand on the thermal stability of MS1, Table 3 summarizes the kinetic parameters of the MS1!GS reaction for a series of complexes with the same ligand environment (NH 3 , ethylenediamine and pyridine in the equatorial position) and charge. Earlier, the influence of the trans-to-NO ligand in trans-[RuNO(NH 3 ) 4 X] 2+ on the activation energy of the MS1!GS reaction was investigated by density functional theory (DFT) calculations (Yamaletdinov & Zilberberg, 2017). According to that work, E a increases in the sequence X = SH À , OH À , Cl À , F À and equals 0.66, 0.97, 1.04 and 1.24 eV, respectively.…”

The impact of counterion on the metastable state properties of nitrosyl ruthenium complexes

“…UV/vis spectra of A(ClO 4 ) 2 at 10 K exhibit broad band in low-energy range with maximum at 410 nm related to the charge transfer from trans-to-NO ligand (fluoride) to π * (Ru-NO) orbital (Fig. 9) 35 . In DCSs additional bands appears at: 600, 520 and 460 nm in case of A[PdCl 4 ] (Fig.…”

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis

“…Regardless of the broad application of DFT method in chemistry, few cases addressed linkage isomerism in coordination compounds, and even fewer used the NBO approach …”

“…The energy difference from the Pauliviolating orbital and the actual energy gives the effect of steric repulsion. [31,32,41,42] Regardless of the broad application of DFT method in chemistry, few cases addressed linkage isomerism in coordination compounds, [21,[43][44][45][46][47][48][49][50][51][52][53][54][55][56][57] and even fewer used the NBO approach. [58][59][60][61][62] There are plenty schemes of energy decomposition analysis (EDA) besides the first proposed by Morokuma.…”