title: Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory.
abstract: 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=CR'R''), such as benzophenone, aldehydes, paraformaldehyde or CO2, to give [Cp2Zr(OCR'R''PR2)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(μ-OCHPhPCy2)][MeB(C6F5)3]}2 (10a) with chalcone results in 1,4 addition of the Zr(+)/P FLP, whereas the reaction of {[Cp2Zr(μ-OCHFcPCy2)][MeB(C6F5)3]}2 (11a; Fc=(C5H4)CpFe) with [Pd(η(3)C3H5)Cl]2 yields the unique Zr-Fe-Pd trimetallic complex 13a, which has been characterised by XRD analysis.
authors: Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany. adrien.normand@u-bourgogne.fr.|ICMUB, Université de Bourgogne Franche-comté, UFR Sciences et Techniques, 9 avenue Alain Savary - BP, 47870 21078, Dijon Cedex, France. adrien.normand@u-bourgogne.fr.
authors: Adrien T
authors: http://orcid.org/0000-0002-8047-9386
authors: AT
authors: Normand
authors: Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
authors: Constantin G
authors: CG
authors: Daniliuc
authors: Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
authors: Birgit
authors: B
authors: Wibbeling
authors: Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
authors: Gerald
authors: G
authors: Kehr
authors: ICMUB, Université de Bourgogne Franche-comté, UFR Sciences et Techniques, 9 avenue Alain Savary - BP, 47870 21078, Dijon Cedex, France. pierre.le-gendre@u-bourgogne.fr.
authors: Pierre
authors: P
authors: Le Gendre
authors: Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
authors: Gerhard
authors: G
authors: Erker
keywords: ambiphilic ligands; frustrated Lewis pairs; insertion; phosphides; zirconium