6533b7dcfe1ef96bd1273380

RESEARCH PRODUCT

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

Birgit WibbelingGerald KehrAdrien T. NormandAdrien T. NormandConstantin G. DaniliucGerhard ErkerPierre Le Gendre

subject

Steric effectsChalconeStereochemistryzirconiumc-h activation010402 general chemistry01 natural sciencesMedicinal chemistry[ CHIM ] Chemical SciencesCatalysisFrustrated Lewis pairinsertionchemistry.chemical_compoundCyclopentadienyl complexx-ray structuresphosphinidene complexesBenzophenone[CHIM]Chemical SciencesParaformaldehydezr-p bondzirconocene-phosphido complexesmolecular-structure010405 organic chemistryLigandphosphidesOrganic ChemistryCationic polymerizationcrystal-structureGeneral Chemistry0104 chemical sciencesfunctionalized ligandsbis(trimethylsilyl)phosphido complexeschemistryfrustrated Lewis pairsphosphinoaryloxide complexesambiphilic ligands

description

International audience; 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.

yearjournalcountryeditionlanguage
2016-02-11
https://hal-univ-bourgogne.archives-ouvertes.fr/hal-01400485