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 language | English |
|---|---|
| Pages (from-to) | 16878-16884 |
| Number of pages | 7 |
| Journal | Dalton Transactions |
| Volume | 46 |
| Issue number | 48 |
| DOIs | |
| Publication status | Published - Jan 1 2017 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - NO disproportionation by a {RhNO}9 pincer-type complex
AU - Gaviglio, Carina
AU - Pellegrino, Juan
AU - Milstein, David
AU - Doctorovich, Fabio
PY - 2017/1/1
Y1 - 2017/1/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85038397267&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85038397267&partnerID=8YFLogxK
U2 - 10.1039/c7dt03944a
DO - 10.1039/c7dt03944a
M3 - Article
AN - SCOPUS:85038397267
VL - 46
SP - 16878
EP - 16884
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 48
ER -