Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-

Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) data of a unique family of complexes of nitroso compounds coordinated to pentachloroiridate(III), [Cl5IrN(O)XR] 2- (X = NH, S, CH and R = alkyl, aryl) are presented. These novel complexes are obtained by nucl...

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Autores principales: Escola, Natalia, Di Salvo, Florencia, Perissinotti, Laura L., Doctorovich, Fabio Ariel
Publicado: 2007
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v46_n12_p4827_Escola
http://hdl.handle.net/20.500.12110/paper_00201669_v46_n12_p4827_Escola
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_00201669_v46_n12_p4827_Escola2023-06-08T14:40:35Z Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2- Escola, Natalia Di Salvo, Florencia Perissinotti, Laura L. Doctorovich, Fabio Ariel Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) data of a unique family of complexes of nitroso compounds coordinated to pentachloroiridate(III), [Cl5IrN(O)XR] 2- (X = NH, S, CH and R = alkyl, aryl) are presented. These novel complexes are obtained by nucleophilic attack of primary amines, thiols, and alkenes to the coordinated nitrosyl. Despite their lability and low volatility, MS analysis of complexes of the type MN(O)X was done for the first time, complementing other spectroscopic techniques. The intrinsic dissociation chemistry of the gaseous diagnostic ions was studied via ESI-MS/MS and found to be very useful to confirm the proposed connectivities of the parent complexes. In particular, ESI-MS of their solutions allows the detection of series of diagnostic ions, mainly, [M - Cl]-, [M + K]-, [M - NO]-•, and [M - Cl + AcN]- (AcN = acetonitrile), which confirmed the identity of the analyzed complexes to be M = [Cl 5IrN(O)XR]2-. Major fragments were formed by losses of NO or N(O)XR. ESI-MS and ESI-MS/MS measurements are therefore shown to be the proper techniques to complement the spectroscopic characterization of this important class of nitroso complexes. An interesting rearrangement that does not take place in solution was observed in the gaseous phase, and a plausible mechanism is discussed. © 2007 American Chemical Society. Fil:Escola, N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Di Salvo, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Perissinotti, L. 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_00201669_v46_n12_p4827_Escola http://hdl.handle.net/20.500.12110/paper_00201669_v46_n12_p4827_Escola
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) data of a unique family of complexes of nitroso compounds coordinated to pentachloroiridate(III), [Cl5IrN(O)XR] 2- (X = NH, S, CH and R = alkyl, aryl) are presented. These novel complexes are obtained by nucleophilic attack of primary amines, thiols, and alkenes to the coordinated nitrosyl. Despite their lability and low volatility, MS analysis of complexes of the type MN(O)X was done for the first time, complementing other spectroscopic techniques. The intrinsic dissociation chemistry of the gaseous diagnostic ions was studied via ESI-MS/MS and found to be very useful to confirm the proposed connectivities of the parent complexes. In particular, ESI-MS of their solutions allows the detection of series of diagnostic ions, mainly, [M - Cl]-, [M + K]-, [M - NO]-•, and [M - Cl + AcN]- (AcN = acetonitrile), which confirmed the identity of the analyzed complexes to be M = [Cl 5IrN(O)XR]2-. Major fragments were formed by losses of NO or N(O)XR. ESI-MS and ESI-MS/MS measurements are therefore shown to be the proper techniques to complement the spectroscopic characterization of this important class of nitroso complexes. An interesting rearrangement that does not take place in solution was observed in the gaseous phase, and a plausible mechanism is discussed. © 2007 American Chemical Society.
author Escola, Natalia
Di Salvo, Florencia
Perissinotti, Laura L.
Doctorovich, Fabio Ariel
spellingShingle Escola, Natalia
Di Salvo, Florencia
Perissinotti, Laura L.
Doctorovich, Fabio Ariel
Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
author_facet Escola, Natalia
Di Salvo, Florencia
Perissinotti, Laura L.
Doctorovich, Fabio Ariel
author_sort Escola, Natalia
title Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
title_short Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
title_full Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
title_fullStr Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
title_full_unstemmed Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl 5]2-
title_sort electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [ircl 5]2-
publishDate 2007
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v46_n12_p4827_Escola
http://hdl.handle.net/20.500.12110/paper_00201669_v46_n12_p4827_Escola
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