Diverse C -Coordination Modes of NHC-Tricyclohexylphosphonium Ylide Ligands in Palladium(II) Complexes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2022

Diverse C -Coordination Modes of NHC-Tricyclohexylphosphonium Ylide Ligands in Palladium(II) Complexes

Résumé

Thanks to the +PCy3 substituents which are unlikely to undergo intramolecular C–H activation, the Pd(II) complex [(C,C,C)PdCl](OTf) having a neutral LX2-type NHC, diphosphonium bis(ylide) pincer ligand was selectively prepared by a double deprotonation of the [(NHC)PdCl2(Py)] precursor with tBuOK. The influence of the +PCy3 substituents on the overall electronic properties of this pincer scaffold was evaluated by IR spectroscopy data of the corresponding Pd–CO adduct, revealing its stronger electron-donating character in comparison to the structurally related NHC core pincer bearing +PPh3 extremities. Treatment of the electron-rich pincer complex [(C,C,C)PdCl](OTf) with AgOTf led to the C,C-chelating NHC-phosphonium ylide Pd(II) complex [(C,C)Pd(OTf)Cl](OTf) via the oxidatively induced homolytic cleavage of a Pd–ylide bond. In the presence of a stronger base (KHMDS or LDA) cyclometalation of a +P–Cy substituent was observed, affording a constrained Pd(II) complex featuring the unique anionic LX3-type C,C,C,C-NHC, diphosphonium tris(ylide) ligand.
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Dates et versions

hal-03579686 , version 1 (18-02-2022)

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Mustapha El Kadiri, Abdelali Chihab, Rachid Taakili, Carine Duhayon, Dmitry A. Valyaev, et al.. Diverse C -Coordination Modes of NHC-Tricyclohexylphosphonium Ylide Ligands in Palladium(II) Complexes. Organometallics, 2022, 41 (4), pp.456-466. ⟨10.1021/acs.organomet.1c00700⟩. ⟨hal-03579686⟩
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