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

Carina Gaviglio, Juan Pellegrino, David Milstein, Fabio Doctorovich

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)16878-16884
Number of pages7
JournalDalton Transactions
Volume46
Issue number48
DOIs
Publication statusPublished - Jan 1 2017

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Ligands
Nitrites
Discrete Fourier transforms
Nuclear magnetic resonance
Infrared radiation
X ray diffraction
X rays
Molecules
Geometry
Experiments

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Gaviglio, C., Pellegrino, J., Milstein, D., & Doctorovich, F. (2017). NO disproportionation by a {RhNO}9 pincer-type complex. Dalton Transactions, 46(48), 16878-16884. https://doi.org/10.1039/c7dt03944a

NO disproportionation by a {RhNO}9 pincer-type complex. / Gaviglio, Carina; Pellegrino, Juan; Milstein, David; Doctorovich, Fabio.

In: Dalton Transactions, Vol. 46, No. 48, 01.01.2017, p. 16878-16884.

Research output: Contribution to journalArticle

Gaviglio, C, Pellegrino, J, Milstein, D & Doctorovich, F 2017, 'NO disproportionation by a {RhNO}9 pincer-type complex', Dalton Transactions, vol. 46, no. 48, pp. 16878-16884. https://doi.org/10.1039/c7dt03944a
Gaviglio, Carina ; Pellegrino, Juan ; Milstein, David ; Doctorovich, Fabio. / NO disproportionation by a {RhNO}9 pincer-type complex. In: Dalton Transactions. 2017 ; Vol. 46, No. 48. pp. 16878-16884.
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