Bonding Mode of a Bifunctional P~Si-H ligand in the Ruthenium Complex "Ru(PPh2CH2OSiMe2H)3".

Virginia Montiel-Palma (1) , Olivier Piechaczyk (2) , Alexandre Picot (1) , Audrey Auffrant (2) , Laure Vendier (1) , Pascal Le Floch (2) , Sylviane Sabo-Etienne (1)

1 LCC - Laboratoire de chimie de coordination
2 DCPH - Laboratoire Hétéroéléments et Coordination

The phosphinosilane compound PPh2CH2OSiMe2H is potentially a bifunctional P∼Si−H ligand. By treatment with the RuII precursor RuH2(H2)2(PCy3)2, the complex Ru(PPh2CH2OSiMe2H)3 (2), resulting from the coordination of three ligands and the displacement of two PCy3 and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P∼Si−H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si−H group, whereas the two others act as bidentate ligands with different Si−H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)ruthenium(IV) species (form 2a) resulting from two Si−H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si−H bond and only one oxidative addition.

Domaines: Chimie de coordination

Virginia Montiel-Palma, Olivier Piechaczyk, Alexandre Picot, Audrey Auffrant, Laure Vendier, et al.. Bonding Mode of a Bifunctional P~Si-H ligand in the Ruthenium Complex "Ru(PPh2CH2OSiMe2H)3".. Inorganic Chemistry, 2008, 47 (19), pp.8601-8603. ⟨10.1021/ic801327a⟩. ⟨hal-00320384⟩