Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands

The synthesis, properties and reactivity of monocyclopentadienyltitanium(III) complexes stabilized by hydridoborato (BH3R)‒ ligands are reported. The reactions of the titanium(IV) trichlorides [Ti(h5-C5H5-nMen)Cl3] with excess LiBH3R (R = H, Me) afford dimeric [{Ti(h5-C5H5-nMen)(BH4)(μ-BH4)}2] (n =...

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Autores: Calvo-Molina, Adrián, Del Horno, Estefanía, Jover Modrego, Jesús, Pérez-Redondo, Adrián, Yélamos, Carlos, Zapata, Rosa
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/200460
Acceso en línea:https://hdl.handle.net/2445/200460
Access Level:acceso abierto
Palabra clave:Titani
Lligands
Cristal·lografia
Titanium
Ligands
Crystallography
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spelling Monocyclopentadienyltitanium(III) Complexes with Hydridoborato LigandsCalvo-Molina, AdriánDel Horno, EstefaníaJover Modrego, JesúsPérez-Redondo, AdriánYélamos, CarlosZapata, RosaTitaniLligandsCristal·lografiaTitaniumLigandsCrystallographyThe synthesis, properties and reactivity of monocyclopentadienyltitanium(III) complexes stabilized by hydridoborato (BH3R)‒ ligands are reported. The reactions of the titanium(IV) trichlorides [Ti(h5-C5H5-nMen)Cl3] with excess LiBH3R (R = H, Me) afford dimeric [{Ti(h5-C5H5-nMen)(BH4)(μ-BH4)}2] (n = 5 (1), 4 (2), 0 (3)) or monomeric [Ti(h5-C5Me5)(BH3Me)2] (4) titanium(III) derivatives. Compound 3 is a thermally unstable oil and decomposes at room temperature forming a mixed-valence TiII/TiIII tetrametallic species [{Ti(h5-C5H5)(BH4)}2{(μ3-B2H6)Ti(h5-C5H5)}2] (5) with dianionic diborane(6) ligands in a rare μ3-k2:k2:k2-B2H6 coordination mode. DFT calculations for 5 agree with a triplet ground state with two inner titanium(II) atoms bonded by a single bond and two outer titanium(III) centers. In contrast to 3, the monomeric tetrahydrofuran adduct derivative [Ti(h5-C5H5)(BH4)2(thf)] (6) is a stable solid. Dimeric 1-3 react with 2,6-lutidinium salts (LutH)X (X = BPh4, OSO2CF3) to afford ion pairs, [Ti(h5-C5H5-nMen)(BH4)L2](BPh4) (L = thf, n = 5 (7), 4 (8), 0 (9); L = py, n = 5 (10)), or molecular aggregates, [{Ti(h5-C5Me5)(BH4)(μ-O2SOCF3)}2] (11) and [{Ti(h5-C5H5-nMen)(μ-O2SOCF3)2}x] (n = 5, x = 3 (12); n = 4, x = 4 (13)), via formation of H2 and (Lut)BH3. Diamagnetic titanium(II) derivatives [{Ti(h5-C5Me5)(μ-H)}2{(μ-H)2Al(BH3R)(thf)}2] (R = H (14), Me (15)) were isolated in reactions of complexes 1 and 4 with LiAlH4 in tetrahydrofuran.American Chemical Society2023202320232023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersion13 p.application/pdfhttps://hdl.handle.net/2445/200460Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésReproducció del document publicat a: https://doi.org/10.1021/acs.organomet.2c00580Organometallics, 2023, vol. 42, p. 1360-1372https://doi.org/10.1021/acs.organomet.2c00580cc-by (c) Calvo-Molina, Adrián et al., 2023http://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccessoai:recercat.cat:2445/2004602026-05-29T05:05:01Z
dc.title.none.fl_str_mv Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
title Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
spellingShingle Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
Calvo-Molina, Adrián
Titani
Lligands
Cristal·lografia
Titanium
Ligands
Crystallography
title_short Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
title_full Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
title_fullStr Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
title_full_unstemmed Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
title_sort Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands
dc.creator.none.fl_str_mv Calvo-Molina, Adrián
Del Horno, Estefanía
Jover Modrego, Jesús
Pérez-Redondo, Adrián
Yélamos, Carlos
Zapata, Rosa
author Calvo-Molina, Adrián
author_facet Calvo-Molina, Adrián
Del Horno, Estefanía
Jover Modrego, Jesús
Pérez-Redondo, Adrián
Yélamos, Carlos
Zapata, Rosa
author_role author
author2 Del Horno, Estefanía
Jover Modrego, Jesús
Pérez-Redondo, Adrián
Yélamos, Carlos
Zapata, Rosa
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Titani
Lligands
Cristal·lografia
Titanium
Ligands
Crystallography
topic Titani
Lligands
Cristal·lografia
Titanium
Ligands
Crystallography
description The synthesis, properties and reactivity of monocyclopentadienyltitanium(III) complexes stabilized by hydridoborato (BH3R)‒ ligands are reported. The reactions of the titanium(IV) trichlorides [Ti(h5-C5H5-nMen)Cl3] with excess LiBH3R (R = H, Me) afford dimeric [{Ti(h5-C5H5-nMen)(BH4)(μ-BH4)}2] (n = 5 (1), 4 (2), 0 (3)) or monomeric [Ti(h5-C5Me5)(BH3Me)2] (4) titanium(III) derivatives. Compound 3 is a thermally unstable oil and decomposes at room temperature forming a mixed-valence TiII/TiIII tetrametallic species [{Ti(h5-C5H5)(BH4)}2{(μ3-B2H6)Ti(h5-C5H5)}2] (5) with dianionic diborane(6) ligands in a rare μ3-k2:k2:k2-B2H6 coordination mode. DFT calculations for 5 agree with a triplet ground state with two inner titanium(II) atoms bonded by a single bond and two outer titanium(III) centers. In contrast to 3, the monomeric tetrahydrofuran adduct derivative [Ti(h5-C5H5)(BH4)2(thf)] (6) is a stable solid. Dimeric 1-3 react with 2,6-lutidinium salts (LutH)X (X = BPh4, OSO2CF3) to afford ion pairs, [Ti(h5-C5H5-nMen)(BH4)L2](BPh4) (L = thf, n = 5 (7), 4 (8), 0 (9); L = py, n = 5 (10)), or molecular aggregates, [{Ti(h5-C5Me5)(BH4)(μ-O2SOCF3)}2] (11) and [{Ti(h5-C5H5-nMen)(μ-O2SOCF3)2}x] (n = 5, x = 3 (12); n = 4, x = 4 (13)), via formation of H2 and (Lut)BH3. Diamagnetic titanium(II) derivatives [{Ti(h5-C5Me5)(μ-H)}2{(μ-H)2Al(BH3R)(thf)}2] (R = H (14), Me (15)) were isolated in reactions of complexes 1 and 4 with LiAlH4 in tetrahydrofuran.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/200460
url https://hdl.handle.net/2445/200460
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1021/acs.organomet.2c00580
Organometallics, 2023, vol. 42, p. 1360-1372
https://doi.org/10.1021/acs.organomet.2c00580
dc.rights.none.fl_str_mv cc-by (c) Calvo-Molina, Adrián et al., 2023
http://creativecommons.org/licenses/by/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) Calvo-Molina, Adrián et al., 2023
http://creativecommons.org/licenses/by/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 13 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.811543

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