DFT study of metastable linkage isomers six-coordinate ruthenium nitrosyl complexes

摘要

The linkage isomers of the [M(NO)(CN)_5]~(2-) (M = Fe, Ru, Os), [Ru(NO)Cl_5~](2-), trans-[Ru(NO)(NH_3)_4(L)]~(q+) = NH_,3, H_2O nicotinamide, imidazole, pyridine, pyratine, NO_2 - (a,O)-,4OndH t)r~aCnqs (-HL[R ,=ul(N~O)~L_ pyridine, NO_2-) 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 η~l--2iNnkOag aen Oids oηm~e1rs, 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)Cl_-]52 comp~lexes were found. The calculations of infrared spectra of linkage isomers [Ru(NO)Cl_-a]252 raen cda r[Rr~ieud(N oOut).( -CThNe)_analysis of quantum chemical bond orders indicates a noticeable delocalization of π-electron density along the L trans- M - NO axis and a possibility of direct interactions between NO and equatorial ligands in the structures with the bent { MNO} group.