Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes

The reactions of nitrido complexes [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) and [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) with electrophilic reagents ROTf (R = H, Me; OTf = OSO2CF3) in different molar ratios have allowed the structural characterization of a series of titanium intermediates en route to the format...

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Authors: Barriopedro Torres, Paula, Caballo González, Jorge, Mena Montoro, Miguel|||0000-0001-7456-1212, Pérez Redondo, Adrián|||0000-0002-0086-8825, Yélamos Sánchez, Carlos|||0000-0003-0425-4799
Format: article
Publication Date:2020
Country:España
Institution:Universidad de Alcalá (UAH)
Repository:e_Buah Biblioteca Digital Universidad de Alcalá
Language:English
OAI Identifier:oai:ebuah.uah.es:10017/43509
Online Access:http://hdl.handle.net/10017/43509
https://dx.doi.org/10.1021/acs.inorgchem.0c00550
Access Level:Open access
Keyword:Química
Chemistry
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spelling Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium ComplexesBarriopedro Torres, PaulaCaballo González, JorgeMena Montoro, Miguel|||0000-0001-7456-1212Pérez Redondo, Adrián|||0000-0002-0086-8825Yélamos Sánchez, Carlos|||0000-0003-0425-4799QuímicaChemistryThe reactions of nitrido complexes [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) and [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) with electrophilic reagents ROTf (R = H, Me; OTf = OSO2CF3) in different molar ratios have allowed the structural characterization of a series of titanium intermediates en route to the formation of the ammonium salts [NR4]OTf and [NR4][Ti(eta5-C5Me5)(OTf)4]. The treatment of the trinuclear imido-nitrido complex 1 with 5.5 equiv of triflic acid in toluene at room temperature led to the dinuclear complex [Ti2(eta5-C5Me5)2(mu-N)(NH3)(mu-O2SOCF3)2(OTf)] (3) and [NH4]OTf. Compound 3, along with the ammonium salts [NMe4]OTf and [NMe4][Ti(eta5-C5Me5)(OTf)4] (5), was also obtained in the reaction of 1 with 8 equiv of methyl triflate in toluene at 100 °C. The trinuclear complex [Ti3(eta5-C5Me5)3(mu-N)(mu-NH)2(mu-O2SOCF3)(OTf)] (4), an intermediate in the formation of 3, was isolated in the treatment of 1 with 4 equiv of MeOTf, although compound 4 was prepared in better yield by treatment of 1 with Me3SiOTf (2 equiv). Addition of a large excess of MeOTf or HOTf reagents to solutions of 3 resulted in the clean formation of ammonium salts [NR4][Ti(eta5-C5Me5)(OTf)4] (R = Me (5), H (6)). Treatment of the tetranuclear nitrido complex [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) with 1 equiv of ROTf in toluene afforded the precipitation of the ionic compounds [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NR)][OTf] (R = H (8), Me (9)), while a large excess of HOTf led to the formation of [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NH)][Ti(eta5-C5Me5)(OTf)4(NH3)] (10) by rupture of a fraction of tetranuclear molecules. Complex 2 reacted with 1 equiv of [M(eta5-C5H5)(CO)3H] (M = Mo, Cr) via hydrogenation of one nitrido ligand to give the molecular derivative [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NH)] (11) and [{M(eta5-C5H5)(CO)3}2], while a second 1 equiv of [M(eta5-C5H5)(CO)3H] produced the ionic compounds....Ministerio de Ciencia, Innovación y UniversidadesMinisterio de Educación y CienciaUniversidad de Alcalá20202020-06-0120202020-06-0120212021-06-02journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10017/43509https://dx.doi.org/10.1021/acs.inorgchem.0c00550reponame:e_Buah Biblioteca Digital Universidad de Alcaláinstname:Universidad de Alcalá (UAH)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:ebuah.uah.es:10017/435092026-06-18T11:13:07Z
dc.title.none.fl_str_mv Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
title Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
spellingShingle Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
Barriopedro Torres, Paula
Química
Chemistry
title_short Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
title_full Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
title_fullStr Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
title_full_unstemmed Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
title_sort Successive Protonation and Methylation of Bridging Imido and Nitrido Ligands at Titanium Complexes
dc.creator.none.fl_str_mv Barriopedro Torres, Paula
Caballo González, Jorge
Mena Montoro, Miguel|||0000-0001-7456-1212
Pérez Redondo, Adrián|||0000-0002-0086-8825
Yélamos Sánchez, Carlos|||0000-0003-0425-4799
author Barriopedro Torres, Paula
author_facet Barriopedro Torres, Paula
Caballo González, Jorge
Mena Montoro, Miguel|||0000-0001-7456-1212
Pérez Redondo, Adrián|||0000-0002-0086-8825
Yélamos Sánchez, Carlos|||0000-0003-0425-4799
author_role author
author2 Caballo González, Jorge
Mena Montoro, Miguel|||0000-0001-7456-1212
Pérez Redondo, Adrián|||0000-0002-0086-8825
Yélamos Sánchez, Carlos|||0000-0003-0425-4799
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química
Chemistry
topic Química
Chemistry
description The reactions of nitrido complexes [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) and [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) with electrophilic reagents ROTf (R = H, Me; OTf = OSO2CF3) in different molar ratios have allowed the structural characterization of a series of titanium intermediates en route to the formation of the ammonium salts [NR4]OTf and [NR4][Ti(eta5-C5Me5)(OTf)4]. The treatment of the trinuclear imido-nitrido complex 1 with 5.5 equiv of triflic acid in toluene at room temperature led to the dinuclear complex [Ti2(eta5-C5Me5)2(mu-N)(NH3)(mu-O2SOCF3)2(OTf)] (3) and [NH4]OTf. Compound 3, along with the ammonium salts [NMe4]OTf and [NMe4][Ti(eta5-C5Me5)(OTf)4] (5), was also obtained in the reaction of 1 with 8 equiv of methyl triflate in toluene at 100 °C. The trinuclear complex [Ti3(eta5-C5Me5)3(mu-N)(mu-NH)2(mu-O2SOCF3)(OTf)] (4), an intermediate in the formation of 3, was isolated in the treatment of 1 with 4 equiv of MeOTf, although compound 4 was prepared in better yield by treatment of 1 with Me3SiOTf (2 equiv). Addition of a large excess of MeOTf or HOTf reagents to solutions of 3 resulted in the clean formation of ammonium salts [NR4][Ti(eta5-C5Me5)(OTf)4] (R = Me (5), H (6)). Treatment of the tetranuclear nitrido complex [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) with 1 equiv of ROTf in toluene afforded the precipitation of the ionic compounds [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NR)][OTf] (R = H (8), Me (9)), while a large excess of HOTf led to the formation of [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NH)][Ti(eta5-C5Me5)(OTf)4(NH3)] (10) by rupture of a fraction of tetranuclear molecules. Complex 2 reacted with 1 equiv of [M(eta5-C5H5)(CO)3H] (M = Mo, Cr) via hydrogenation of one nitrido ligand to give the molecular derivative [{Ti(eta5-C5Me5)}4(mu3-N)3(mu3-NH)] (11) and [{M(eta5-C5H5)(CO)3}2], while a second 1 equiv of [M(eta5-C5H5)(CO)3H] produced the ionic compounds....
publishDate 2020
dc.date.none.fl_str_mv 2020
2020-06-01
2020
2020-06-01
2021
2021-06-02
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10017/43509
https://dx.doi.org/10.1021/acs.inorgchem.0c00550
url http://hdl.handle.net/10017/43509
https://dx.doi.org/10.1021/acs.inorgchem.0c00550
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:e_Buah Biblioteca Digital Universidad de Alcalá
instname:Universidad de Alcalá (UAH)
instname_str Universidad de Alcalá (UAH)
reponame_str e_Buah Biblioteca Digital Universidad de Alcalá
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