S. A. Kuklin, Pavel V. Petrovskii, Fedor M. Dolgushin, Miguel Baya, Aleksey M. Sheloumov, A.A. Koridze, Veronika Yu. Lagunova, Irina I. Petukhova, Alexander S. Peregudov, Evgenii V. Vorontsov, Mariam G. Ezernitskaya, Rinaldo Poli, Ivane Javakhishvili Tbilisi State University (TSU), A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences [Moscow] (RAS), 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 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), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), 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), and 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)
International audience; Palladium P,C,P pincer complexes based on ferrocene were synthesized for the first time. The reaction of the 1,3-bis((dialkylphosphino)methyl)ferrocenes {1,3-(R2PCH2)2C5H3}Fe(C5H5) (2a, R = Pri; 2b, R = But) with PdCl2(NCPh)2 in refluxing 2-methoxyethanol leads to the corresponding pincer complexes PdCl[{2,5-(R2PCH2)2C5H2}Fe(C5H5)] (3a,b). The ferrocene-based binuclear compound 3b reacts with [Cp2Fe]PF6 to form the ferrocenium-based pincer complex {PdCl[{2,5-(But2PCH2)2C5H2}Fe(C5H5)]}PF6 (4b), and this is the first example of ferrocene-based phosphine chelate oxidation centered on the iron atom. Treatment of complexes 3a,b with NaBH4 in refluxing ethanol affords the complexes Pd(BH4)[{2,5-(R2PCH2)2C5H2}Fe(C5H5)] (5a, R = Pri; 5b, R = But), containing a BH4− group coordinated to the metal in the rarely occurring unidentate mode. The structures of 3a,b and 5b were confirmed by X-ray analyses. Cyclic voltammetric investigations of complexes 2b and 3a,b are also reported. The structural and spectroscopic features of the palladium ferrocene-based pincer complexes are discussed and compared with those of related compounds.