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Issue 48, 2017
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NO˙ disproportionation by a {RhNO}9 pincer-type complex

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Abstract

The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)]˙ () 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 . Infrared spectroscopic experiments with -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.

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

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Publication details

The article was received on 19 Oct 2017, accepted on 17 Nov 2017 and first published on 17 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT03944A
Citation: Dalton Trans., 2017,46, 16878-16884
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    NO˙ disproportionation by a {RhNO}9 pincer-type complex

    C. Gaviglio, J. Pellegrino, D. Milstein and F. Doctorovich, Dalton Trans., 2017, 46, 16878
    DOI: 10.1039/C7DT03944A

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