The Effect of trans Ligands in the NO-Linkage Reverse Isomerization for Ruthenium–Nitrosyl–Tetraammine Complexes:
A DFT Study
European Journal of Inorganic Chemistry
, E-ISSN: 1099-0682
||Charge transfer, Density functional calculations, Metastable compounds, Ruthenium, Thermal decay
Yamaletdinov Ruslan D.
Zilberberg Igor L.
Nikolaev Institute of Inorganic Chemistry, Lavrentieva 3, Novosibirsk 630090, Russian Federation
Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk 630090, Russian Federation
Federal Agency for Scientific Organizations
The rearrangement of the NO ligand in ruthenium–nitrosyl–tetraammine complexestrans-
[Ru(NO)(NH3)4X]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 ligand-to-metal charge transfer of the p(X)→π*(Ru–ON) type. The excitation energy for electron transfer fromp-orbital of ligand to LUMO correlates perfectly with the activation energy of isomerization. Found correlations are explained in terms of electronegativity of thetrans ligand X.