NO˙ disproportionation by a {RhNO} 9 pincer-type complex

DOCTOROVICH, FABIO; PELLEGRINO, JUAN; GAVIGLIO, CARINA; MILSTEIN, DAVID

DALTON TRANSACTIONS

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2017 vol. 46 p. 16878 - 16884

1477-9226

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.