An Infrared Study of Gas-Phase Metal Nitrosyl Ion-Molecule Complexes.

ABSTRACT: We present a combined experimental and quantum chemical study of gas-phase group 9 metal nitrosyl complexes, M(NO)_n⁺ (M = Co, Rh, Ir). Experimental infrared photodissociation spectra of mass-selected ion-molecule complexes are presented in the region 1600 cm^-1 to 2000 cm^-1 which includes the NO stretch. These are interpreted by comparison with the simulated spectra of energetically low-lying structures calculated using density functional theory. A mix of linear and nonlinear ligand binding is observed, often within the same complex, and clear evidence of coordination shell closing is observed at n = 4 for Co(NO)_n⁺ and Ir(NO)_n⁺. Calculations of Rh(NO)_n⁺ complexes suggest additional low-lying five-coordinate structures. In all cases, once a second coordination shell is occupied, new spectral features appear which are assigned to (NO)₂ dimer moieties. Further evidence of such motifs comes from differences in the spectra recorded in the dissociation channels corresponding to single and double ligand loss.

SUBMITTER: Meizyte G 

PROVIDER: S-EPMC9791661 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature