Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the...

Autores: Bolzán, Agustín Eduardo; Güida, Jorge Alberto; Piatti, Roberto C. V.; Arvia, Alejandro Jorge; Piro, Oscar Enrique; Sabino, J. R; Castellano, Eduardo Ernesto
Año de publicación: 2007
Idioma: inglés
Tipo de recurso: artículo
Estado: versión publicada
Descripción: The N,N,N′,N′-tetramethylformamidinium disulphide (TMFDS) was prepared from either the electro-oxidation of tetramethylthiourea (TMTU) on platinum electrodes in aqueous perchloric acid solution or the chemical oxidation of TMTU with hydrogen peroxide in hydrochloric acid-containing absolute ethanol. The electrochemical formation of TMFDS at different potentials was followed by in situ FTIRRAS spectroscopy. The IR and Raman spectra of TMFDS chemically formed as a chloride dihydrate were determined and compared to the product produced electrochemically. The crystal structure of the chloride salt [N(CH₃)₂]₂C=S-S=C [N(CH₃)₂]₂Cl₂·2H₂O, as determined by X-ray diffraction, crystallises in the monoclinic C2/c space group with a = 23.267(1), b = 10.824(1), c = 17.774(1) Å, β = 126.91(1)°, and Z = 8. The structure was solved from 2489 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0405. The two molecular halves of the dimeric $[N ({CH}_{3})_{2}]_{2} CSSC [N ({CH}_{3})_{2}]_{2}^{2 +}$ ion are linked by a disulphide single bond [d(S-S) = 2.0454(9) Å] and related to each other by a non-crystallographic pseudo two-fold axis. DFT structure optimisation and normal mode frequencies were calculated using the 6-311G(d,f) basis set at DFT theory level. An estimation of the free energy for the dimer formation and rate ratio for the homogeneous and heterogeneous processes are presented. These data are consistent with the electrochemical mechanism of the anodic formation of TMFDS²⁺ from TMTU electro-oxidation in acid solutions.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia: Ciencias Exactas
Química
Tetramethylthiourea
DFT
Vibrational spectra
Crystal structure
Oxidation
Formamidinium disulphide
Electrochemistry
Nivel de accesibilidad: acceso abierto
Condiciones de uso: http://creativecommons.org/licenses/by/4.0/
Repositorio
Institución: Universidad Nacional de La Plata
OAI Identificador: oai:sedici.unlp.edu.ar:10915/121090

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oai_identifier_str	oai:sedici.unlp.edu.ar:10915/121090
network_acronym_str	SEDICI
repository_id_str	1329
network_name_str	SEDICI (UNLP)
spelling	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate saltBolzán, Agustín EduardoGüida, Jorge AlbertoPiatti, Roberto C. V.Arvia, Alejandro JorgePiro, Oscar EnriqueSabino, J. RCastellano, Eduardo ErnestoCiencias ExactasQuímicaTetramethylthioureaDFTVibrational spectraCrystal structureOxidationFormamidinium disulphideElectrochemistryThe N,N,N′,N′-tetramethylformamidinium disulphide (TMFDS) was prepared from either the electro-oxidation of tetramethylthiourea (TMTU) on platinum electrodes in aqueous perchloric acid solution or the chemical oxidation of TMTU with hydrogen peroxide in hydrochloric acid-containing absolute ethanol. The electrochemical formation of TMFDS at different potentials was followed by in situ FTIRRAS spectroscopy. The IR and Raman spectra of TMFDS chemically formed as a chloride dihydrate were determined and compared to the product produced electrochemically. The crystal structure of the chloride salt [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>C=S-S=C [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>Cl<sub>2</sub>·2H<sub>2</sub>O, as determined by X-ray diffraction, crystallises in the monoclinic C2/c space group with a = 23.267(1), b = 10.824(1), c = 17.774(1) Å, β = 126.91(1)°, and Z = 8. The structure was solved from 2489 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0405. The two molecular halves of the dimeric <math><mrow is="true"><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><mtext is="true"><mtext>C</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/sbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>C</mtext></mtext><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msubsup is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow><mrow is="true"><mn is="true">2</mn><mo is="true">+</mo></mrow></msubsup></mrow></math> ion are linked by a disulphide single bond [d(S-S) = 2.0454(9) Å] and related to each other by a non-crystallographic pseudo two-fold axis. DFT structure optimisation and normal mode frequencies were calculated using the 6-311G(d,f) basis set at DFT theory level. An estimation of the free energy for the dimer formation and rate ratio for the homogeneous and heterogeneous processes are presented. These data are consistent with the electrochemical mechanism of the anodic formation of TMFDS<sup>2+</sup> from TMTU electro-oxidation in acid solutions.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2007info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf131-139http://sedici.unlp.edu.ar/handle/10915/121090enginfo:eu-repo/semantics/altIdentifier/issn/0022-2860info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2007.02.004info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/4.0/Creative Commons Attribution 4.0 International (CC BY 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2026-05-27T11:22:53Zoai:sedici.unlp.edu.ar:10915/121090Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292026-05-27 11:22:53.912SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
title	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
spellingShingle	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt Bolzán, Agustín Eduardo Ciencias Exactas Química Tetramethylthiourea DFT Vibrational spectra Crystal structure Oxidation Formamidinium disulphide Electrochemistry
title_short	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
title_full	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
title_fullStr	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
title_full_unstemmed	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
title_sort	Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the chloride dihydrate salt
dc.creator.none.fl_str_mv	Bolzán, Agustín Eduardo Güida, Jorge Alberto Piatti, Roberto C. V. Arvia, Alejandro Jorge Piro, Oscar Enrique Sabino, J. R Castellano, Eduardo Ernesto
author	Bolzán, Agustín Eduardo
author_facet	Bolzán, Agustín Eduardo Güida, Jorge Alberto Piatti, Roberto C. V. Arvia, Alejandro Jorge Piro, Oscar Enrique Sabino, J. R Castellano, Eduardo Ernesto
author_role	author
author2	Güida, Jorge Alberto Piatti, Roberto C. V. Arvia, Alejandro Jorge Piro, Oscar Enrique Sabino, J. R Castellano, Eduardo Ernesto
author2_role	author author author author author author
dc.subject.none.fl_str_mv	Ciencias Exactas Química Tetramethylthiourea DFT Vibrational spectra Crystal structure Oxidation Formamidinium disulphide Electrochemistry
topic	Ciencias Exactas Química Tetramethylthiourea DFT Vibrational spectra Crystal structure Oxidation Formamidinium disulphide Electrochemistry
dc.description.none.fl_txt_mv	The N,N,N′,N′-tetramethylformamidinium disulphide (TMFDS) was prepared from either the electro-oxidation of tetramethylthiourea (TMTU) on platinum electrodes in aqueous perchloric acid solution or the chemical oxidation of TMTU with hydrogen peroxide in hydrochloric acid-containing absolute ethanol. The electrochemical formation of TMFDS at different potentials was followed by in situ FTIRRAS spectroscopy. The IR and Raman spectra of TMFDS chemically formed as a chloride dihydrate were determined and compared to the product produced electrochemically. The crystal structure of the chloride salt [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>C=S-S=C [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>Cl<sub>2</sub>·2H<sub>2</sub>O, as determined by X-ray diffraction, crystallises in the monoclinic C2/c space group with a = 23.267(1), b = 10.824(1), c = 17.774(1) Å, β = 126.91(1)°, and Z = 8. The structure was solved from 2489 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0405. The two molecular halves of the dimeric <math><mrow is="true"><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><mtext is="true"><mtext>C</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/sbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>C</mtext></mtext><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msubsup is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow><mrow is="true"><mn is="true">2</mn><mo is="true">+</mo></mrow></msubsup></mrow></math> ion are linked by a disulphide single bond [d(S-S) = 2.0454(9) Å] and related to each other by a non-crystallographic pseudo two-fold axis. DFT structure optimisation and normal mode frequencies were calculated using the 6-311G(d,f) basis set at DFT theory level. An estimation of the free energy for the dimer formation and rate ratio for the homogeneous and heterogeneous processes are presented. These data are consistent with the electrochemical mechanism of the anodic formation of TMFDS<sup>2+</sup> from TMTU electro-oxidation in acid solutions. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
description	The N,N,N′,N′-tetramethylformamidinium disulphide (TMFDS) was prepared from either the electro-oxidation of tetramethylthiourea (TMTU) on platinum electrodes in aqueous perchloric acid solution or the chemical oxidation of TMTU with hydrogen peroxide in hydrochloric acid-containing absolute ethanol. The electrochemical formation of TMFDS at different potentials was followed by in situ FTIRRAS spectroscopy. The IR and Raman spectra of TMFDS chemically formed as a chloride dihydrate were determined and compared to the product produced electrochemically. The crystal structure of the chloride salt [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>C=S-S=C [N(CH<sub>3</sub>)<sub>2</sub>]<sub>2</sub>Cl<sub>2</sub>·2H<sub>2</sub>O, as determined by X-ray diffraction, crystallises in the monoclinic C2/c space group with a = 23.267(1), b = 10.824(1), c = 17.774(1) Å, β = 126.91(1)°, and Z = 8. The structure was solved from 2489 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0405. The two molecular halves of the dimeric <math><mrow is="true"><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><mtext is="true"><mtext>C</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/sbnd"></mglyph><mtext>S</mtext><mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/dbnd"></mglyph><mtext>C</mtext></mtext><mo stretchy="false" is="true">[</mo><mtext is="true">N</mtext><mo stretchy="false" is="true">(</mo><msub is="true"><mrow is="true"><mtext is="true">CH</mtext></mrow><mrow is="true"><mn is="true">3</mn></mrow></msub><msub is="true"><mrow is="true"><mo stretchy="false" is="true">)</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow></msub><msubsup is="true"><mrow is="true"><mo stretchy="false" is="true">]</mo></mrow><mrow is="true"><mn is="true">2</mn></mrow><mrow is="true"><mn is="true">2</mn><mo is="true">+</mo></mrow></msubsup></mrow></math> ion are linked by a disulphide single bond [d(S-S) = 2.0454(9) Å] and related to each other by a non-crystallographic pseudo two-fold axis. DFT structure optimisation and normal mode frequencies were calculated using the 6-311G(d,f) basis set at DFT theory level. An estimation of the free energy for the dimer formation and rate ratio for the homogeneous and heterogeneous processes are presented. These data are consistent with the electrochemical mechanism of the anodic formation of TMFDS<sup>2+</sup> from TMTU electro-oxidation in acid solutions.
publishDate	2007
dc.date.none.fl_str_mv	2007
dc.type.none.fl_str_mv	info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Articulo http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo
format	article
status_str	publishedVersion
dc.identifier.none.fl_str_mv	http://sedici.unlp.edu.ar/handle/10915/121090
url	http://sedici.unlp.edu.ar/handle/10915/121090
dc.language.none.fl_str_mv	eng
language	eng
dc.relation.none.fl_str_mv	info:eu-repo/semantics/altIdentifier/issn/0022-2860 info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2007.02.004
dc.rights.none.fl_str_mv	info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/4.0/ Creative Commons Attribution 4.0 International (CC BY 4.0)
eu_rights_str_mv	openAccess
rights_invalid_str_mv	http://creativecommons.org/licenses/by/4.0/ Creative Commons Attribution 4.0 International (CC BY 4.0)
dc.format.none.fl_str_mv	application/pdf 131-139
dc.source.none.fl_str_mv	reponame:SEDICI (UNLP) instname:Universidad Nacional de La Plata instacron:UNLP
reponame_str	SEDICI (UNLP)
collection	SEDICI (UNLP)
instname_str	Universidad Nacional de La Plata
instacron_str	UNLP
institution	UNLP
repository.name.fl_str_mv	SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv	alira@sedici.unlp.edu.ar
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score	12.98848

Formation of N,N,N′,N′-tetramethylformamidinium disulphide from the chemical and electrochemical oxidation of tetramethylthiourea : Vibrational spectra and crystal structure of the...

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