Amb motiu del tancament d'estiu, la validació de documents es reprendrà a partir del 28 d'agost de 2026. Disculpeu les molèsties.
Con motivo del cierre de verano, la validación de documentos se reanudará a partir del 28 de agosto de 2026. Disculpad las molestias
Due to the summer closure, document validation will resume starting August 28, 2026. We apologize for any inconvenience.

Fitxers

896425.pdf (2.49 MB)

Tipus de document

Article

Versió

Versió publicada

Data de publicació

2025-05-31

Llicència de publicació

cc-by (c) Calvo-Molina, A. et al., 2025
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/222143

Revisiting the structure and properties of mid-valent monopentamethylcyclopentadienylchromium complexes

Títol de la revista

Autors

Director/Tutor

ISSN de la revista

Títol del volum

Recurs relacionat

https://doi.org/https://doi.org/10.1039/D5DT00620A

Resum

The structure and properties of half-sandwich chromium complexes derived from the dinuclear chloride compound [{CrCp*(μ-Cl)}2] (1) (Cp* = η5-C5Me5) are revisited. Complex 1 does not react with H2 and N2 but cleaves the nitrogen–nitrogen bonds of azobenzene and 1,2-diphenylhydrazine at room temperature to give dinuclear chromium(IV) bis(imido) [{CrCp*Cl(μ-NPh)}2] (2) and chromium(III) bis(amido) [{CrCp*Cl(μ-NHPh)}2] (3) derivatives, respectively. Reactions of 1 with cyclopentyllithium [Li(C5H9)] in hexane or toluene under reflux conditions afford the previously reported tetranuclear chromium(II) hydride complex [{CrCp*(μ3-H)}4] (4) and the unsymmetrical chromium(I) sandwich compound [CrCp*(η6-C6H5Me)] (5) as crystals suitable for X-ray diffraction studies. While the treatment of 1 with excess LiBH4 leads to an analogous dinuclear complex [{CrCp*(μ-κ3-BH4)}2] (6), the reaction of the chromium(III) compound [{CrCp*Cl(μ-Cl)}2] with LiBH4 gives the mononuclear species [CrCp*(κ2-BH4)2] (7). Complex 6 cleanly reacts with the 2,6-lutidinium salt (LutH)(BPh4) to form the zwitterionic sandwich derivative [CrCp*(η6-C6H5-BPh3)] (8). Compounds 1 and 6 react with LiAlH4 to give a diamagnetic tetrachromium aggregate [(Al{(μ-H)4CrCp*})4] (9), which can be described as low-spin chromate(II) {CrCp*H4}3− units stabilizing the Al3+ ions primarily through Cr–H → Al interactions and weaker Cr → Al donation according to density functional theory (DFT) calculations. The thermal decomposition of 9 in benzene at 90 °C affords a mixed-valence CrII/CrI hexachromium species [(Al2{(μ-H)4CrCp*}{(μ3-H)4Cr2Cp*2})2] (10) with analogous interactions of {CrCp*H4}3− and {Cr2Cp*2H4}3− units with Al3+ ions.

Matèries

Crom, Clorurs, Metalls de transició

Matèries (anglès)

Chromium, Chlorides, Transition metals

Citació

Col·leccions

Articles publicats en revistes (Química Inorgànica i Orgànica)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citació

CALVO-MOLINA, Adrián, et al. Revisiting the structure and properties of mid-valent monopentamethylcyclopentadienylchromium complexes. Dalton Transactions. 2025. Vol. 54, num. 20, pags. 8190-8023. ISSN 1477-9226. [consulted: 8 of August of 2026]. Available at: https://hdl.handle.net/2445/222143

Exportar metadades

JSON - METS

Compartir registre