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

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.

Automated summary

This study presents a combined experimental and quantum chemical investigation of group 9 metal nitrosyl complexes in the gas phase. Experimental infrared photodissociation spectra of mass-selected ion-molecule complexes are analyzed using simulated spectra of low-lying structures calculated using density functional theory. The results reveal a mixture of linear and nonlinear ligand binding, as well as evidence of coordination shell closing. Additional low-lying five-coordinate structures are suggested for Rh(NO)n+ complexes. Spectral features attributed to (NO)2 dimer moieties appear once a second coordination shell is occupied. Differences in spectra recorded in dissociation channels correspond to single and double ligand loss provide further evidence of such motifs.