Combined experimental/computational study of iridium and palladium hydride PP(O)P pincer complexes

C. Martin , Sonia Mallet-Ladeira , Karinne Miqueu (1) , G. Bouhadir (2) , D. Bourissou (2)

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
2 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée

The diphosphine-phosphine oxide \[o-iPr2P(C6H 4)]2P(=O)H\ (1) has been prepared, and its coordination to Ir and Pd has been explored. Using [IrCl(cyclooctene)2]2, the pincer hydride complex \(o-iPr2PC6H4) 2P(O)]IrHCl\ (2) is readily obtained by phosphine-assisted P(O)-H bond activation. Coordination of CO to Ir affords the corresponding octahedral complex \(o-iPr2PC6H4)2P(O)] IrHCl(CO)\ (3) as a single stereoisomer. The electronic properties of the PP(O)P ligand have been compared with those of related PEP frameworks on the basis of νCO stretching frequencies. Treatment of 1 with [Pd(PtBu 3)2] gives the palladium hydride complex \(o-iPr 2PC6H4)2P(O)]PdH\ (4). The mechanism of P(O)-H bond activation at Pd has been investigated computationally. Complex 4 reacts with methyl acrylate at room temperature, giving \(o-iPr 2PC6H4)2P(O)]PdCH(Me)CO 2Me\ (7) as the result of regioselective insertion into the Pd-H bond. © 2014 American Chemical Society.

Domaines: Chimie

C. Martin, Sonia Mallet-Ladeira, Karinne Miqueu, G. Bouhadir, D. Bourissou. Combined experimental/computational study of iridium and palladium hydride PP(O)P pincer complexes. Organometallics, 2014, 33 (2), pp.571--577. ⟨10.1021/om401117d⟩. ⟨hal-01505912⟩