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

TFG_QU Ates Ceresuela, Ulunay.pdf (1.25 MB)

Tipus de document

Treball de fi de grau

Data de publicació

2019-01

Llicència de publicació

cc-by-nc-nd (c) Ates, 2019
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/128822

Synthesis and characterization of cyclometallated complexes of imines: 4-ClC6H4CH=NCH2(4’-FC6H4) and 2,3-F2C6H3CH=NCH2(4’-FC6H4). Expanding the scope of cyclopalladations

Títol de la revista

Autors

Director/Tutor

ISSN de la revista

Títol del volum

Recurs relacionat

Resum

The treatment of 4-fluorobenzylamine with 4-chlorobenzaldehyde or 2,3-difluorobenzaldehyde in acetone at 80ºC afforded the corresponding imines (1), 4-ClC6H4CH=NCH2(4’-FC6H4) and 2,3-F2C6H3CH=NCH2(4’-FC6H4) respectively, which were isolated in a yield >90%. The same reaction was performed in milder conditions obtaining similar results. The imines (1) reacted with a stoichiometric amount of Pd(OAc)2 in acetic acid affording the corresponding acetato-bridged five-membered ortho-cyclopalladated dimers (2) in 44-69% yield. The reaction was reproduced in different conditions to improve the yield, obtaining the best results at 85ºC for 1h. Compounds 2 were converted by a metathesis reaction with an excess of LiCl and LiBr in acetone into the corresponding chloro- or bromo-bridged dinuclear cyclopalladated compounds. The stoichiometric amount of PPh3 and dppe was added to the halogen-bridge compounds to obtain the mononuclear compounds trans-N,L-[Pd{RHC=NCH2(4’-FC6H4)}(X)(L)] [3-A (R= 4-ClC6H4, X= Br, L= PPh3); 3-B (R= 2,3-F2C6H3, X = Br, L = PPh3); 4-A (R= 4-ClC6H4, X= Cl, L= PPh3); and the dinuclear compounds 5-A (R= 4-ClC6H4, X= Br, L= dppe); 5-B (R= 2,3-F2C6H3, X= Br, L= dppe)] in 50-90% yield. The compounds obtained were characterized by 1H NMR, 31P NMR spectroscopy −in CDCl3 solution−, elemental analyses, mass spectrometry, and IR spectroscopy. Some tendencies have been found in this work: i) the E isomer of the imine was isolated in all reactions; ii) the ortho-fluoro atoms show an interaction with the imine proton; iii) the endo-palladacycle is the thermodynamic control isomer; iv) the aromatic protons of the metallated ring are high field shifted in compounds containing phosphines, showing a trans arrangement between the phosphines and the nitrogen atom in agreement with the transphobia; v) the methinic proton signal in proton NMR spectra is displaced toward high fields confirming the nitrogen-metal bond.

Descripció

Treballs Finals de Grau de Química, Facultat de Química, Universitat de Barcelona, Any: 2019, Tutor: Jaume Granell Sanvicente

Matèries

Imines, Fosfina, Treballs de fi de grau

Matèries (anglès)

Imines, Phosphine, Bachelor's theses

Citació

Col·leccions

Treballs Finals de Grau (TFG) - Química

Citació

ATES CERESUELA, Ulunay. Synthesis and characterization of cyclometallated complexes of imines: 4-ClC6H4CH=NCH2(4’-FC6H4) and 2,3-F2C6H3CH=NCH2(4’-FC6H4). Expanding the scope of cyclopalladations. [consulted: 12 of August of 2026]. Available at: https://hdl.handle.net/2445/128822

Exportar metadades

JSON - METS

Compartir registre