Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory

Adrien T. Normand (1, 2) , Constantin G. Daniliuc (1) , Birgit Wibbeling (1) , Gerald Kehr (1) , Pierre Le gendre (2) , Gerhard Erker (1)

1 Organisch-Chemisches Institut Munster
2 ICMUB - Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon]

Neutral phosphidozirconocene complexes [Cp2Zr(PR2)Me] (Cp=cyclopentadienyl; 1a: R=cyclohexyl (Cy); 1b: R=mesityl (Mes); 1c: R=tBu) undergo insertion into the Zr-P bond by non-enolisable carbonyl building blocks (O=CRR), such as benzophenone, aldehydes, paraformaldehyde or CO2, to give [Cp2Zr(OCRRPR2)Me] (3-7). Depending on the steric bulk around P, complexes 3-7 react with B(C6F5)(3) to give O-bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp2Zr(-OCHPhPCy2)][MeB(C6F5)(3)]}(2) (10a) with chalcone results in 1,4 addition of the Zr+/P FLP, whereas the reaction of {[Cp2Zr(-OCHFcPCy(2))][MeB(C6F5)(3)]}(2) (11a; Fc=(C5H4)CpFe) with [Pd((3)-C3H5)Cl](2) yields the unique Zr-Fe-Pd trimetallic complex 13a, which has been characterised by XRD analysis.

Mots clés: ambiphilic ligands; frustrated Lewis pairs; insertion; phosphides; zirconium; zr-p bond; zirconocene-phosphido complexes; x-ray structures; c-h activation; molecular-structure; crystal-structure; bis(trimethylsilyl)phosphido complexes; phosphinoaryloxide complexes; phosphinidene complexes; functionalized ligands

Domaines: Chimie

Adrien T. Normand, Constantin G. Daniliuc, Birgit Wibbeling, Gerald Kehr, Pierre Le gendre, et al.. Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory. Chemistry - A European Journal, 2016, 22 (12), pp.4285 - 4293. ⟨10.1002/chem.201504792⟩. ⟨hal-01400485⟩