CH bond activation of unsaturated hydrocarbons by a niobium methyl cyclopropyl precursor. Cyclopropyl ring opening and alkyne coupling reaction

Pascal Oulié (1, 2) , Chiara Dinoi (1, 2) , Chen Li (1, 2) , Alix Sournia-Saquet (1) , Kane Jacob (1) , Laure Vendier (1) , Michel Etienne (1, 2)

1 LCC - Laboratoire de chimie de coordination
2 UT3 - Université Toulouse III - Paul Sabatier

The transient intermediate η2-cyclopropene/bicyclobutane niobium complex [TpMe2Nb(η2-c-C3H4)(MeCCMe)] A, generated by an intramolecular β-H abstraction of methane from the methyl cyclopropyl complex [TpMe2NbMe(c-C3H5)(MeCCMe)] (1), is able to cleave the CH bond of a variety of unsaturated hydrocarbons RH in a selective manner to give the corresponding hydrocarbyl complexes [TpMe2NbR(c-C3H5)(MeCCMe)] (R = 2-furyl, 2-thienyl, 1-alkynyl, 1-cyclopentenyl, 1-ferrocenyl (Fc), pentafluorophenyl). The activation of the C–H bond occurs stereospecifically via a 1,3-CH addition across the Nb(η2-cyclopropene) bond of A. Full characterization of several of these complexes includes multinuclear NMR spectroscopy, X-ray diffraction, UV/vis spectroscopy, and electrochemical data. A charge transfer between the ferrocenyl moiety and the niobium center is responsible for the characteristic purple color of the bimetallic complex [TpMe2NbFc(c-C3H5)(MeCCMe)]. The reactivity of these complexes with benzene follows qualitatively the strength and the pKa of the CH bond that is cleaved. The pentafluorophenyl complex [TpMe2Nb(C6F5)(c-C3H5)(MeCCMe)] undergoes cyclopropyl ring opening and alkyne coupling to give two isomeric η4-butadienyl complexes, with [TpMe2Nb(C6F5)(η4-CMeCMeCHCHMe)] as the major isomer.

Domaines: Chimie de coordination

Pascal Oulié, Chiara Dinoi, Chen Li, Alix Sournia-Saquet, Kane Jacob, et al.. CH bond activation of unsaturated hydrocarbons by a niobium methyl cyclopropyl precursor. Cyclopropyl ring opening and alkyne coupling reaction. Organometallics, 2017, 36 (1), pp.53-63. ⟨10.1021/acs.organomet.6b00506⟩. ⟨hal-01939584⟩