Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations
Predominantly No-centered reduction was observed by EPR and IR spectroelectrochemistry to occur reversibly at low temperatures for [Cl 5Ir(NO)]-. In contrast, the [Cl5Ru(NO)] 2- ion was found to undergo only irreversible reduction but reversible oxidation to a ruthenium(III) species at -40°C. DFT ca...
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paper:paper_14779226_v_n12_p1797_Sieger2023-06-08T16:18:18Z Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations Escola, Natalia Doctorovich, Fabio Ariel Olabe Iparraguirre, Jose Antonio Anisotropy Chlorine compounds Electrolysis Electrolytic reduction Electronic structure Iridium Oxidation Paramagnetic resonance Probability density function Ruthenium Transition metals IR spectroelectrochemistry Reduction-induced dissociation Stretching frequencies Zero order regular approximations (ZORA) Nitrogen oxides Predominantly No-centered reduction was observed by EPR and IR spectroelectrochemistry to occur reversibly at low temperatures for [Cl 5Ir(NO)]-. In contrast, the [Cl5Ru(NO)] 2- ion was found to undergo only irreversible reduction but reversible oxidation to a ruthenium(III) species at -40°C. DFT calculations were used to establish the electronic structures and to rationalise the different stabilities. The calculations also reveal orientation-dependent energies and EPR properties between staggered and eclipsed conformations. © The Royal Society of Chemistry 2004. Fil:Escola, N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2004 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n12_p1797_Sieger http://hdl.handle.net/20.500.12110/paper_14779226_v_n12_p1797_Sieger |
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Universidad de Buenos Aires |
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I-28 |
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R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Anisotropy Chlorine compounds Electrolysis Electrolytic reduction Electronic structure Iridium Oxidation Paramagnetic resonance Probability density function Ruthenium Transition metals IR spectroelectrochemistry Reduction-induced dissociation Stretching frequencies Zero order regular approximations (ZORA) Nitrogen oxides |
| spellingShingle |
Anisotropy Chlorine compounds Electrolysis Electrolytic reduction Electronic structure Iridium Oxidation Paramagnetic resonance Probability density function Ruthenium Transition metals IR spectroelectrochemistry Reduction-induced dissociation Stretching frequencies Zero order regular approximations (ZORA) Nitrogen oxides Escola, Natalia Doctorovich, Fabio Ariel Olabe Iparraguirre, Jose Antonio Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| topic_facet |
Anisotropy Chlorine compounds Electrolysis Electrolytic reduction Electronic structure Iridium Oxidation Paramagnetic resonance Probability density function Ruthenium Transition metals IR spectroelectrochemistry Reduction-induced dissociation Stretching frequencies Zero order regular approximations (ZORA) Nitrogen oxides |
| description |
Predominantly No-centered reduction was observed by EPR and IR spectroelectrochemistry to occur reversibly at low temperatures for [Cl 5Ir(NO)]-. In contrast, the [Cl5Ru(NO)] 2- ion was found to undergo only irreversible reduction but reversible oxidation to a ruthenium(III) species at -40°C. DFT calculations were used to establish the electronic structures and to rationalise the different stabilities. The calculations also reveal orientation-dependent energies and EPR properties between staggered and eclipsed conformations. © The Royal Society of Chemistry 2004. |
| author |
Escola, Natalia Doctorovich, Fabio Ariel Olabe Iparraguirre, Jose Antonio |
| author_facet |
Escola, Natalia Doctorovich, Fabio Ariel Olabe Iparraguirre, Jose Antonio |
| author_sort |
Escola, Natalia |
| title |
Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| title_short |
Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| title_full |
Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| title_fullStr |
Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| title_full_unstemmed |
Establishing the NO oxidation state in complexes [Cl5(NO)M] n-, M = Ru or Ir, through experiments and DFT calculations |
| title_sort |
establishing the no oxidation state in complexes [cl5(no)m] n-, m = ru or ir, through experiments and dft calculations |
| publishDate |
2004 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n12_p1797_Sieger http://hdl.handle.net/20.500.12110/paper_14779226_v_n12_p1797_Sieger |
| work_keys_str_mv |
AT escolanatalia establishingthenooxidationstateincomplexescl5nomnmruorirthroughexperimentsanddftcalculations AT doctorovichfabioariel establishingthenooxidationstateincomplexescl5nomnmruorirthroughexperimentsanddftcalculations AT olabeiparraguirrejoseantonio establishingthenooxidationstateincomplexescl5nomnmruorirthroughexperimentsanddftcalculations |
| _version_ |
1768545389596639232 |