Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes - Archive ouverte HAL Accéder directement au contenu
Communication Dans Un Congrès Année : 2023

Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes

Résumé

Phosphonium ylides and iminophosphorane were discovered more than 100 years ago by the same authors,1 and exploited since then in organic chemistry via Wittig type reactions for the formation respectively of C=C and C=N bonds.2 The strong electron density at the ylidic atom as pointed out by the zwitterionic canonical forms (Figure 1) makes them electron donating ligands in coordination chemistry. In this study we aimed at comparing for the first time the electronic properties of iminophosphorane and phosphonium ylides.3 For that purpose, we synthesized dicarbonyl rhodium(I) complexes featuring a rigid phosphine-ylide ligand formed on the ortho-phenylene skeleton In this communication we will compare the donating ability of both ylides based on experimental data as well as Density Functional Theory (DFT) calculations. In particular the influence of the substituent on the ylidic atom will be pointed out. [1] Staudinger, H.; Meyer, J. Über Neue Organische Phosphorverbindungen III. Phosphinmethylenderivate Und Phosphinimine. Helv. Chim. Acta 1919, 2 (1), 635–646. [2] Komen, C. M. D. Ylides and Imines of Phosphorus A.W. Johnson John Wiley & Sons Ltd, Chichester, Recl. Trav. Chim. Pays-Bas 1994, 113 (7–8), 382–382. [3] Popovici, I.; Barthes, C.; Tannoux, T.; Duhayon, C.; Casaretto, N.; Monari, A.; Auffrant, A.; Canac, Y. Inorg. Chem. accepté

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Dates et versions

hal-04547541 , version 1 (15-04-2024)

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  • HAL Id : hal-04547541 , version 1

Citer

Ingrid Popovici, Cécile Barthes, Thibault Tannoux, Carine Duhayon, Nicolas Casaretto, et al.. Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes. European Workshop on Phosphorus Chemistry EWPC17, Mar 2023, San Sebastian, Spain. ⟨hal-04547541⟩
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