Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis -[Phosphine-Ylide Rh(CO) 2 ] Complexes
In: ISSN: 0020-1669, 2023
Online
academicJournal
Zugriff:
International audience ; The coordinating properties of two families of ylides, namely, phosphonium ylides and iminophosphoranes, differently substituted at the ylidic center (CH2– vs NiPr–), have been investigated in structurally related cationic phosphine-ylide Rh(CO)2 complexes obtained from readily available phosphine-phosphonium salt precursors derived from an ortho-phenylene bridge. However, while the Rh(CO)2 complex bearing the P+–CH2– donor moiety proved to be stable, the P═NiPr donor end appeared to induce lability to one of the CO groups. All of the RhI carbonyl complexes in both ylide series were fully characterized, including through X-ray diffraction analysis. Based on the experimental and calculated infrared (IR) CO stretching frequencies in Rh(CO)2 complexes, we evidenced that the phosphonium ylide ligand is a stronger donor than the iminophosphorane ligand. However, we also found that the difference in the intrinsic electronic properties can be largely compensated by the introduction of an iPr substituent on the N atom of the iminophosphorane, hence pointing to the noninnocent role of the peripheral substituent and opening novel possibilities to tune the properties of metal complexes containing ylide ligands.
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Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis -[Phosphine-Ylide Rh(CO) 2 ] Complexes
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Autor/in / Beteiligte Person: | Popovici, Ingrid ; Tannoux, Thibault ; Barthes, Cécile ; Duhayon, Carine ; Casaretto, Nicolas ; Monari, Antonio ; Auffrant, Audrey ; Canac, Yves ; Laboratoire de chimie moléculaire (LCM) ; École polytechnique (X)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS) ; Laboratoire de chimie de coordination (LCC) ; Institut de Chimie de Toulouse (ICT) ; Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) ; Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP) ; Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) ; Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS) ; Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)) ; Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité) ; Centre National de la Recherche Scientifique (CNRS) ; polytechnique, Ecole ; ANR-21-CE07-0026,LYMACATO,Ligands ylure et Métaux abondants pour la Catalyse et l'Optique(2021) ; ANR-10-LABX-0096,SEAM,Science and Engineering for Advanced Materials and devices(2010) ; ANR-18-IDEX-0001,Université de Paris,Université de Paris(2018) ; ANR-11-IDEX-0002,UNITI,Université Fédérale de Toulouse(2011) |
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Zeitschrift: | ISSN: 0020-1669, 2023 |
Veröffentlichung: | HAL CCSD ; American Chemical Society, 2023 |
Medientyp: | academicJournal |
DOI: | 10.1021/acs.inorgchem.2c04151 |
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