1. An insight into the structure of model germaphosphaallenes
- Author
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Henri Ranaivonjatovo, Petronela M. Petrar, Ioan Silaghi-Dumitrescu, Jean Escudié, Gabriela Nemes, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Babes bolyai, UNIVERSITE KOGALNICEANU, Department of Chemistry, Babes-Bolyai University [Cluj-Napoca] (UBB), 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 du CNRS (INC)-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), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Electron density ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,010405 organic chemistry ,Chemistry ,Biophysics ,010402 general chemistry ,Condensed Matter Physics ,Antibonding molecular orbital ,01 natural sciences ,0104 chemical sciences ,Crystallography ,Computational chemistry ,Phosphorus atom ,Physical Sciences ,Electronic effect ,Physical and Theoretical Chemistry ,Molecular Biology ,Lone pair ,ComputingMilieux_MISCELLANEOUS ,Natural bond orbital - Abstract
The geometries of all possible isomers of the model compound H2Ge=C=PH were optimized at the B3LYP/6-31G(d,p) level of the theory. The calculation were repeated at higher correlated methods with similar results and for the the isomers of the methyl-substituted phosphagermaallene MeP=C=GeMe2. As another way to stabilise the P=C=Ge unit consists in the use electronic effects, a NBO study was carried out in order to identify the influence that the nature (electropositive or electronegative) of several substituents would have on the strength of the C=Ge bond. Model compounds HP=C=GeR2 and HP=C=GeRR′ were investigated (R = BH2, CH3, SiH3, NH2, OMe, F; R′ = H). It was found that the main interaction contributing to the weakening of the C=Ge bond is a transfer of electron density from the lone pair of the phosphorus atom to the molecular antibonding orbital localized on the Ge–C bond.
- Published
- 2009
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