1,4-Diethynylbenzene-Bridged [Cp*(dppe)Fe](n+) Units: Effect of 2,5-Ethynyl Groups on the Chemical and Electronic Properties

Autor: Jean-René Hamon, Jean-François Halet, Vincent Dorcet, Samia Kahlal, Thierry Roisnel, Thomas Groizard, Rim Makhoul, Paul Hamon, Claude Lapinte
Přispěvatelé: Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), GENCI (Grand Equipment National de Calcul Intensif) [GENCI A0030807367], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Zdroj: European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry, 2020, 2020 (27), pp.2624-2638. ⟨10.1002/ejic.202000345⟩
European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2020, 2020 (27), pp.2624-2638. ⟨10.1002/ejic.202000345⟩
ISSN: 1434-1948
1099-0682
Popis: International audience; The bis(ironvinylidene) complex [1,4-{Cp*(dppe)Fe=C=CH}(2)-2,5-(C equivalent to CH)(2)-C6H2](PF6)(2) ([2-2H](PF6)(2)) was prepared from 1,2,4,5-tetraethynylbenzene and two equiv. of Cp*(dppe)FeCl in 87 % yield. The reaction is very selective and [2-2H](PF6)(2) is the unique organoiron species to be formed. Deprotonation of [2-2H](PF6)(2) provided the target complex 2 (66 % yield) and subsequent oxidation gave the monocationic and dicationic complexes 2(PF6) and 2(PF6)(2). The new complexes were characterized by ESI-mass spectrometry, IR, multinuclear NMR, ESR and Mossbauer spectroscopy, and XRD analyses on single crystals for [2-2H](PF6)(2) and 2(PF6)(2). The magnetic properties of 2(PF6)(2) were investigated by VT H-1 NMR. The data were analyzed with the support of quantum chemistry calculations. The terminal ethynyl groups on the aromatic ring of the bridge modify the population of the bridge-oxidized state, weaken the electronic communication (H-ab approximate to 601 cm(-1)) and strengthen magnetic coupling interactions (J = -530 cm(-1)) compared to the unsubstituted species (H-ab = 1700 cm(-1) and J = -340 cm(-1), respectively).
Databáze: OpenAIRE
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