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

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...

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Autores principales: Gaviglio, C., Pellegrino, J., Milstein, D., Doctorovich, F.
Formato: JOUR
Materias:
Coordination reactions
Infrared imaging
Ligands
Rhodium
X ray diffraction
Apical positions
DFT calculation
Dinitrosyl complex
Disproportionation reactions
Disproportionations
Infrared spectroscopic
Multinuclear NMR
Square-pyramidal geometry
Rhodium compounds
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_14779226_v46_n48_p16878_Gaviglio
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_14779226_v46_n48_p16878_Gaviglio
record_format dspace
spelling todo:paper_14779226_v46_n48_p16878_Gaviglio2023-10-03T16:19:20Z NO disproportionation by a {RhNO}9 pincer-type complex Gaviglio, C. Pellegrino, J. Milstein, D. Doctorovich, F. Coordination reactions Infrared imaging Ligands Rhodium X ray diffraction Apical positions DFT calculation Dinitrosyl complex Disproportionation reactions Disproportionations Infrared spectroscopic Multinuclear NMR Square-pyramidal geometry Rhodium compounds 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. © 2017 The Royal Society of Chemistry. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14779226_v46_n48_p16878_Gaviglio
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Coordination reactions
Infrared imaging
Ligands
Rhodium
X ray diffraction
Apical positions
DFT calculation
Dinitrosyl complex
Disproportionation reactions
Disproportionations
Infrared spectroscopic
Multinuclear NMR
Square-pyramidal geometry
Rhodium compounds
spellingShingle Coordination reactions
Infrared imaging
Ligands
Rhodium
X ray diffraction
Apical positions
DFT calculation
Dinitrosyl complex
Disproportionation reactions
Disproportionations
Infrared spectroscopic
Multinuclear NMR
Square-pyramidal geometry
Rhodium compounds
Gaviglio, C.
Pellegrino, J.
Milstein, D.
Doctorovich, F.
NO disproportionation by a {RhNO}9 pincer-type complex
topic_facet Coordination reactions
Infrared imaging
Ligands
Rhodium
X ray diffraction
Apical positions
DFT calculation
Dinitrosyl complex
Disproportionation reactions
Disproportionations
Infrared spectroscopic
Multinuclear NMR
Square-pyramidal geometry
Rhodium compounds
description 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. © 2017 The Royal Society of Chemistry.
format JOUR
author Gaviglio, C.
Pellegrino, J.
Milstein, D.
Doctorovich, F.
author_facet Gaviglio, C.
Pellegrino, J.
Milstein, D.
Doctorovich, F.
author_sort Gaviglio, C.
title NO disproportionation by a {RhNO}9 pincer-type complex
title_short NO disproportionation by a {RhNO}9 pincer-type complex
title_full NO disproportionation by a {RhNO}9 pincer-type complex
title_fullStr NO disproportionation by a {RhNO}9 pincer-type complex
title_full_unstemmed NO disproportionation by a {RhNO}9 pincer-type complex
title_sort no disproportionation by a {rhno}9 pincer-type complex
url http://hdl.handle.net/20.500.12110/paper_14779226_v46_n48_p16878_Gaviglio
work_keys_str_mv AT gaviglioc nodisproportionationbyarhno9pincertypecomplex
AT pellegrinoj nodisproportionationbyarhno9pincertypecomplex
AT milsteind nodisproportionationbyarhno9pincertypecomplex
AT doctorovichf nodisproportionationbyarhno9pincertypecomplex
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