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Published on: July 27, 2022
NO˙ disproportionation by a {RhNO}9 pincer-type complex
Carina Gaviglio1, Juan Pellegrino2, David Milstein3
1Comisión Nacional de Energía Atómica, CAC-GIyANN, Departamento de Física de la Materia Condensada, Avenida General Paz 1499, San Martín, 1650, Buenos Aires, Argentina.
Abstract:
The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)]˙ (1˙) with NO˙ was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear NMR techniques, IR and X-ray diffraction. The X-ray structure reveals a square pyramidal geometry with an N-bound nitro ligand trans to the Cipso of the PCP ligand and a bent nitrosyl ligand in the apical position. IR measurement of released N2O confirms that one equivalent forms for each molecule of 1˙. Infrared spectroscopic experiments with 1˙-15NO and 14NO˙ suggest that the reaction occurs through the intermediacy of a dinitrosyl complex. In addition, DFT calculations were performed to provide more evidence on the structure of the intermediates and to support the observed reactivity.
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