DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes
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Olga V. Sizova
Abstract
The linkage isomers of the [M(NO)(CN)5]2− (M = Fe, Ru, Os), [Ru(NO)Cl5]2−, trans-[Ru(NO)(NH3)4(L)]q+ (L = NH3, H2O, nicotinamide, imidazole, pyridine, pyrazine, NO2−, OH−, Cl−), and trans-[Ru(NO)L4(OH)]q (L = pyridine, NO2−) ions are studied by density functional theory. DFT calculations show that the electronic ground-state potential surface of these nitrosyl complexes has the local minima corresponding to η2-NO and η1-O linkage isomers, of which the former is characterized by lower energy. The stationary points on the ground state potential energy surface along the GS → MS2 → MS1 path for the [M(NO)(CN)5]2− (M = Fe, Ru, Os) and [Ru(NO)Cl5]2− complexes were found. The calculations of infrared spectra of linkage isomers [Ru(NO)Cl5]2− and [Ru(NO)(CN)5]2− are carried out. The analysis of quantum chemical bond orders indicates a noticeable delocalization of π-electron density along the Ltrans—M—NO axis and a possibility of direct interactions between NO and equatorial ligands in the structures with the bent {MNO} group.
© Oldenbourg Wissenschaftsverlag
Articles in the same Issue
- Preface: Photocrystallography
- Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements: experimental methodology and results
- Light-induced phase separation (LIPS) into like-spin phases observed by Laue neutron diffraction on a single crystal of [Fe(ptz)6](BF4)2
- Neutron photocrystallography: simulation and experiment
- Static and time-resolved photocrystallographic studies in supramolecular solids
- State of the art and opportunities in probing photoinduced phase transitions in molecular materials by conventional and picosecond X-ray diffraction
- Real-time studies of reversible lattice dynamics by femtosecond X-ray diffraction
- Towards pump-probe resonant X-ray diffraction at femtosecond undulator sources
- Exploiting EXAFS and XANES for time-resolved molecular structures in liquids
- Home-based time-resolved photo small angle X-ray diffraction and its applications
- DFT study of crystalline nitrosyl compounds
- Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them
- DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes
- Excited state isomerization in photochromic ruthenium complexes
- Applications of photocrystallography: a future perspective
Articles in the same Issue
- Preface: Photocrystallography
- Out-of-equilibrium charge density distribution of spin crossover complexes from steady-state photocrystallographic measurements: experimental methodology and results
- Light-induced phase separation (LIPS) into like-spin phases observed by Laue neutron diffraction on a single crystal of [Fe(ptz)6](BF4)2
- Neutron photocrystallography: simulation and experiment
- Static and time-resolved photocrystallographic studies in supramolecular solids
- State of the art and opportunities in probing photoinduced phase transitions in molecular materials by conventional and picosecond X-ray diffraction
- Real-time studies of reversible lattice dynamics by femtosecond X-ray diffraction
- Towards pump-probe resonant X-ray diffraction at femtosecond undulator sources
- Exploiting EXAFS and XANES for time-resolved molecular structures in liquids
- Home-based time-resolved photo small angle X-ray diffraction and its applications
- DFT study of crystalline nitrosyl compounds
- Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them
- DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes
- Excited state isomerization in photochromic ruthenium complexes
- Applications of photocrystallography: a future perspective
