Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(II) metal center and catalytic applications in the transfer hydrogenation of ketones - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Dalton Transactions Année : 2009

Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(II) metal center and catalytic applications in the transfer hydrogenation of ketones

Hadrien Heuclin
  • Fonction : Auteur
Audrey Auffrant
X. F Le Goff
Le Floch Pascal
  • Fonction : Auteur correspondant
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Résumé

A series of mixed tetradentate ligands associating two iminophosphorane moieties with two phosphino, thiophosphino, or phosphine oxide groups (labelled 2, 3,and 4 respectively) have been prepared from the corresponding aminophosphonium derivatives. Their coordination to the iron dichloride metal fragment was achieved using the [FeCl2(THF)1.5] precursor leading to [(P2N2)FeCl2](5), [(S2N2)FeCl2] (6), and [(O2N2)FeCl2](7). These complexes were shown to be paramagnetic. Moreover, those ligands can act as bi, tri or tetradentate, as evidenced by X-ray structure analysis of the complexes, depending on the nature of the pendant PY coordinating ligand (Y = lone pair, S, O). Indeed, while only one phosphorus atom is coordinated to iron in 5 (PNN coordination), no thiophosphine moiety is connected to Fe in 6 (NN coordination), whereas both phosphine oxide arms are linked to the metal in 7 (ONNO) coordination. For ligand 2, coordination reactions were also performed with a non-chlorinated iron precursor (either [Fe(CH3CN)6](BF4)2 or [Fe(H2O)6](BF4)2) leading to complexes 8 and 9 depending on the reaction conditions. The different iron(II) complexes 5–9 were tested in catalytic transfer hydrogenation of acetophenone, and were found to be efficient for reactions carried out at 82 ◦ C

Dates et versions

hal-00399280 , version 1 (26-06-2009)

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Antoine Buchard, Hadrien Heuclin, Audrey Auffrant, X. F Le Goff, Le Floch Pascal. Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(II) metal center and catalytic applications in the transfer hydrogenation of ketones. Dalton Transactions, 2009, pp.1659-1667. ⟨10.1039/b816439h⟩. ⟨hal-00399280⟩
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