Ruthenium agostic (phosphinoaryl)borane complexes: multinuclear solid-state and solution NMR, X-ray and DFT studies

Yann Gloaguen (1) , Gilles Alcaraz (1) , Alban Petit (2) , Eric Clot (2) , Yannick Coppel (1) , Laure Vendier (1) , Sylviane Sabo-Etienne (1)

1 LCC - Laboratoire de chimie de coordination
2 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

The reactivity of the (o-phosphinophenyl)(amino)borane compound HB(NiPr2)C6H4(o-PPh2) prepared from Li(C6H4)PPh2 and HBCl(NiPr2) toward the bis(dihydrogen) complex RuH2(H2)2(PCy3)2 (1) was studied by a combination of DFT, X-ray, and multinuclear NMR techniques including solid-state NMR, a technique rarely employed in organometallic chemistry. The study showed that the complex RuH2{HB(NiPr2)C6H4(o-PPh2)}(PCy3)2 (3), isolated in excellent yield as yellow crystals and characterized by X-ray diffraction, led in solution to PCy3 dissociation and formation of an unsaturated 16-electron complex RuH2{HB(NiPr2)C6H4(o-PPh2)}(PCy3) (4), with a hydride trans to a vacant site. In both cases, the (phosphinoaryl)(amino)borane acts as a bifunctional ligand through the phosphine moiety and a Ru-H-B interaction, thus featuring an agostic interaction.

Domaines: Chimie de coordination; Chimie théorique et/ou physique

Yann Gloaguen, Gilles Alcaraz, Alban Petit, Eric Clot, Yannick Coppel, et al.. Ruthenium agostic (phosphinoaryl)borane complexes: multinuclear solid-state and solution NMR, X-ray and DFT studies. Journal of the American Chemical Society, 2011, 133, pp.17232-17238. ⟨10.1021/ja203828r⟩. ⟨hal-00637828⟩