N-phosphanylformamidines (phosfam) R2′N-C(H)=N-PR 2: One-pot synthesis and versatile protonation reaction
| Autor: | Jean-Marc Sotiropoulos, Stéphanie Bastin, Damien Arquier, Karinne Miqueu, Alain Igau, Laure Vendier, Yamna El-Harouch, Thanh Dung Le, Marie-Christine Weyland |
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| Přispěvatelé: | Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2008 |
| Předmět: |
chemistry.chemical_classification
Double bond 010405 organic chemistry Stereochemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry One-pot synthesis Protonation [CHIM.CATA]Chemical Sciences/Catalysis 010402 general chemistry Cleavage (embryo) Kinetic energy 01 natural sciences 0104 chemical sciences Inorganic Chemistry [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography [CHIM.POLY]Chemical Sciences/Polymers chemistry Nitrogen atom [CHIM.COOR]Chemical Sciences/Coordination chemistry Phosphonium compound Conformational isomerism |
| Zdroj: | European Journal of Inorganic Chemistry European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2008, pp.2577-2583. ⟨10.1002/ejic.200701299⟩ |
| ISSN: | 1434-1948 1099-0682 |
| DOI: | 10.1002/ejic.200701299⟩ |
| Popis: | A straightforward synthesis of unprecedented N-phosphanylformamidines (phosfam), 3a,b has been developed. The single-crystal X-ray study of 3a revealed an E-formamidine stereoisomer. The structural parameters show a strong localization of the C1–N1 double bond in the formamidine pattern. Versatile protonation reactions with HCl on 3a and 3b are reported, leading to P–N cleavage vs. prototropy. Experimental studies and DFT calculations have evidenced that the imino nitrogen atom is the basic center of phosfams 3a and 3b. DFT calculations show that the isomers and rotamers of the N- and P-protonated forms of 8a/9a and 8b/9b are energetically close, which prevents conclusions being drawn on the existence of thermodynamic and/or kinetic products. The accessibility of the anti bonding PN orbital (σ*P1N1) is partly responsible for the cleavage of the PN bond in 8a; 8b possesses a less energetically accessible σ*P1N1 orbital which is consistent with the preservation of the PN bond and the quantitative formation of the corresponding phosphonium compound 9b·Cl.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) |
| Databáze: | OpenAIRE |
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