Artículo
Synthesis and characterization of chiral bidentate bis(N-heterocyclic carbene)-carboxylate palladium and nickel complexes
Autor/es | Sánchez, Adrián
Sánz Garrido, Jorge Carrasco Carrasco, Carlos Jesús Montilla Ramos, Francisco Javier Álvarez González, Eleuterio González Arellano, Camino Flores, Juan Carlos Galindo del Pozo, Agustín |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2022 |
Fecha de depósito | 2022-11-14 |
Publicado en |
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Resumen | Complexes [Pd{(S)-NHCMes,R}2] (R = Me, 2a; iPr, 2b; iBu, 2c) and [Pd{(R)-NHCMes,Me}2] (2a’) were prepared by
reaction of the corresponding imidazolium precursor [ImMes,R] (namely (S)–2-alkyl(3-mesityl-1H-imidazol-3-
iu ... Complexes [Pd{(S)-NHCMes,R}2] (R = Me, 2a; iPr, 2b; iBu, 2c) and [Pd{(R)-NHCMes,Me}2] (2a’) were prepared by reaction of the corresponding imidazolium precursor [ImMes,R] (namely (S)–2-alkyl(3-mesityl-1H-imidazol-3- ium-1-yl)acetate, 1a-c, and (R)-2-methyl(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1a’), with Ag2O and sub- sequent interaction with Pd(OAc)2, under appropriate conditions. Alternatively, complexes 2 were also obtained by treating compounds [ImMes,R], 1, with an in-situ prepared lithium diisopropylamide solution and then reaction with [Pd(OAc)2]. On the other hand, the nickel complex [Ni{(S)-NHCMes,iPr}2], 3b, was synthesized by the interaction of the complex [NiCp2] (Cp = η5-C5H5) with [ImMes,iPr], 1b, in THF. If this reaction was carried out in acetonitrile, a mixture of complex 3b and the cyclopentadienyl monocarbene complex [NiCp{(S)-NHCMes,iPr}], 4b, was obtained. Similarly to 2b, compound 3b was also prepared by the in-situ formation of the carbene [(S)– NHCMes,iPr]- and then reaction with [NiBr2(dme)] (dme = 1,2-dimethoxyethane). Complexes 2, 3 and 4 were obtained with good yields and fully characterized by analytical (HR-ESI and microanalysis), spectroscopic (IR, 1H and 13C NMR and polarimetry) and X-ray methods (2c). In the solid state, 2c is a square planar complex con- taining two [(S)-NHCMes,iBu]- ligands coordinated in a κ2-C,O fashion, where the carbene and carboxylate donors have the expected trans configuration. The existence of two possible conformers of complexes 2 and 3 was analyzed using DFT methods. |
Agencias financiadoras | Ministerio de Ciencia e Innovación (MICIN). España Universidad de Sevilla Universidad de Alcalá Comunidad de Madrid. España |
Identificador del proyecto | PGC2018-093443-B-I00
PID2020-114637GB-I00 CCG20/CC-003 EPU-INV/2020/013 |
Cita | Sánchez, A., Sánz Garrido, J., Carrasco Carrasco, C.J., Montilla Ramos, F.J., Álvarez González, E., González Arellano, C.,...,Galindo del Pozo, A. (2022). Synthesis and characterization of chiral bidentate bis(N-heterocyclic carbene)-carboxylate palladium and nickel complexes. Inorganica Chimica Acta, 537, 120946. https://doi.org/10.1016/j.ica.2022.120946. |
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