Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units
The nitrosyl in [IrCl5(NO)]- is probably the most electrophilic known to date. This fact is reflected by its extremely high IR frequency in the solid state, electrochemical behavior, and remarkable reactivity in solution. PPh4[IrCl5(NO)] forms a crystal in which the [IrCl5(NO)]- anions are in a curi...
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2007
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v13_n30_p8428_DiSalvo http://hdl.handle.net/20.500.12110/paper_09476539_v13_n30_p8428_DiSalvo |
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paper:paper_09476539_v13_n30_p8428_DiSalvo2023-06-08T15:53:56Z Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units Di Salvo, Florencia Escola, Natalia Estrin, Dario Ariel Murgida, Daniel Horacio Doctorovich, Fabio Ariel Electron transfer Iridium, nanostructures Nitrosyl Valence isomerization Electron promotion Electrophils Molecular nanowire Nitrosyl Phenyl rings Electrochemical properties Electronic equipment Ground state Nanowires Negative ions Perturbation techniques Solid state device structures Iridium compounds iridium nanowire article chemistry Fourier analysis oxidation reduction reaction X ray crystallography Crystallography, X-Ray Fourier Analysis Iridium Nanowires Oxidation-Reduction The nitrosyl in [IrCl5(NO)]- is probably the most electrophilic known to date. This fact is reflected by its extremely high IR frequency in the solid state, electrochemical behavior, and remarkable reactivity in solution. PPh4[IrCl5(NO)] forms a crystal in which the [IrCl5(NO)]- anions are in a curious wire-like linear arrangement, in which the distance between the N - O moiety of one anion and the trans chloride of the upper one nearby is only 2.8 Å. For the same complex [IrCl5(NO)]- but with a different counterion, Na[IrCl5(NO)], the anions are stacked one over the other in a side-by-side arrangement. In this case the electronic distribution can be depicted as the closed-shell electronic structure IrIII-NO +, as expected for any d6 third-row transition metal complex. However, in PPh4[IrCl5(NO)] an unprecedented electronic perturbation takes place, probably due to NȮ-Cl- acceptor-donor interactions among a large number of [IrCl5(NO)] - units, favoring a different electronic distribution, namely the open-shell electronic structure IrIV-NȮ. This conclusion is based on XANES experimental evidence, which demonstrates that the formal oxidation state for iridium in PPh4-[IrCl5(NO)] is +4, as compared with + 3 in K[IrCl5(NO)], In agreement, solid-state DFT calculations show that the ground state for [IrCl5(NO)]- in the PPh4+ salt comprises an open-shell singlet with an electronic structure which encompasses half of the spin density mainly localized on a metal-centered orbital, and the other half on an NO-based orbital. The electronic perturbation could be seen as an electron promotion from a metal-chloride to a metal-NO orbital, due to the small HOMO-LUMO gap in PPh 4-[IrCl5(NO)]. This is probably induced by electrostatic interactions acting as a result of the closeness and wire-like spatial arrangement of the Ir metal centers, imposed by lattice forces due to π-π stacking interactions among the phenyl rings in PPh4+. Experimental and theoretical data indicate that in PPh4[IrCl 5(NO)] the Ir - N - O moiety is partially bent and tilted. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA. Fil:Di Salvo, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Escola, N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Murgida, D. 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. 2007 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v13_n30_p8428_DiSalvo http://hdl.handle.net/20.500.12110/paper_09476539_v13_n30_p8428_DiSalvo |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Electron transfer Iridium, nanostructures Nitrosyl Valence isomerization Electron promotion Electrophils Molecular nanowire Nitrosyl Phenyl rings Electrochemical properties Electronic equipment Ground state Nanowires Negative ions Perturbation techniques Solid state device structures Iridium compounds iridium nanowire article chemistry Fourier analysis oxidation reduction reaction X ray crystallography Crystallography, X-Ray Fourier Analysis Iridium Nanowires Oxidation-Reduction |
| spellingShingle |
Electron transfer Iridium, nanostructures Nitrosyl Valence isomerization Electron promotion Electrophils Molecular nanowire Nitrosyl Phenyl rings Electrochemical properties Electronic equipment Ground state Nanowires Negative ions Perturbation techniques Solid state device structures Iridium compounds iridium nanowire article chemistry Fourier analysis oxidation reduction reaction X ray crystallography Crystallography, X-Ray Fourier Analysis Iridium Nanowires Oxidation-Reduction Di Salvo, Florencia Escola, Natalia Estrin, Dario Ariel Murgida, Daniel Horacio Doctorovich, Fabio Ariel Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| topic_facet |
Electron transfer Iridium, nanostructures Nitrosyl Valence isomerization Electron promotion Electrophils Molecular nanowire Nitrosyl Phenyl rings Electrochemical properties Electronic equipment Ground state Nanowires Negative ions Perturbation techniques Solid state device structures Iridium compounds iridium nanowire article chemistry Fourier analysis oxidation reduction reaction X ray crystallography Crystallography, X-Ray Fourier Analysis Iridium Nanowires Oxidation-Reduction |
| description |
The nitrosyl in [IrCl5(NO)]- is probably the most electrophilic known to date. This fact is reflected by its extremely high IR frequency in the solid state, electrochemical behavior, and remarkable reactivity in solution. PPh4[IrCl5(NO)] forms a crystal in which the [IrCl5(NO)]- anions are in a curious wire-like linear arrangement, in which the distance between the N - O moiety of one anion and the trans chloride of the upper one nearby is only 2.8 Å. For the same complex [IrCl5(NO)]- but with a different counterion, Na[IrCl5(NO)], the anions are stacked one over the other in a side-by-side arrangement. In this case the electronic distribution can be depicted as the closed-shell electronic structure IrIII-NO +, as expected for any d6 third-row transition metal complex. However, in PPh4[IrCl5(NO)] an unprecedented electronic perturbation takes place, probably due to NȮ-Cl- acceptor-donor interactions among a large number of [IrCl5(NO)] - units, favoring a different electronic distribution, namely the open-shell electronic structure IrIV-NȮ. This conclusion is based on XANES experimental evidence, which demonstrates that the formal oxidation state for iridium in PPh4-[IrCl5(NO)] is +4, as compared with + 3 in K[IrCl5(NO)], In agreement, solid-state DFT calculations show that the ground state for [IrCl5(NO)]- in the PPh4+ salt comprises an open-shell singlet with an electronic structure which encompasses half of the spin density mainly localized on a metal-centered orbital, and the other half on an NO-based orbital. The electronic perturbation could be seen as an electron promotion from a metal-chloride to a metal-NO orbital, due to the small HOMO-LUMO gap in PPh 4-[IrCl5(NO)]. This is probably induced by electrostatic interactions acting as a result of the closeness and wire-like spatial arrangement of the Ir metal centers, imposed by lattice forces due to π-π stacking interactions among the phenyl rings in PPh4+. Experimental and theoretical data indicate that in PPh4[IrCl 5(NO)] the Ir - N - O moiety is partially bent and tilted. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA. |
| author |
Di Salvo, Florencia Escola, Natalia Estrin, Dario Ariel Murgida, Daniel Horacio Doctorovich, Fabio Ariel |
| author_facet |
Di Salvo, Florencia Escola, Natalia Estrin, Dario Ariel Murgida, Daniel Horacio Doctorovich, Fabio Ariel |
| author_sort |
Di Salvo, Florencia |
| title |
Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| title_short |
Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| title_full |
Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| title_fullStr |
Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| title_full_unstemmed |
Electronic perturbation in a molecular nanowire of [IrCl 5(NO)]- units |
| title_sort |
electronic perturbation in a molecular nanowire of [ircl 5(no)]- units |
| publishDate |
2007 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09476539_v13_n30_p8428_DiSalvo http://hdl.handle.net/20.500.12110/paper_09476539_v13_n30_p8428_DiSalvo |
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