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Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory
Author(s) -
Normand Adrien T.,
Daniliuc Constantin G.,
Wibbeling Birgit,
Kehr Gerald,
Le Gendre Pierre,
Erker Gerhard
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504792
Subject(s) - frustrated lewis pair , steric effects , chemistry , benzophenone , cyclopentadienyl complex , ligand (biochemistry) , paraformaldehyde , cationic polymerization , stereochemistry , medicinal chemistry , crystallography , lewis acids and bases , chalcone , metallocene , photochemistry , polymer chemistry , catalysis , organic chemistry , biochemistry , receptor , polymer , polymerization
Neutral phosphidozirconocene complexes [Cp 2 Zr(PR 2 )Me] (Cp=cyclopentadienyl; 1a : R=cyclohexyl (Cy); 1b : R=mesityl (Mes); 1c : R= t Bu) undergo insertion into the Zr−P bond by non‐enolisable carbonyl building blocks (O=CR′R′′), such as benzophenone, aldehydes, paraformaldehyde or CO 2 , to give [Cp 2 Zr(OCR′R′′PR 2 )Me] ( 3 – 7 ). Depending on the steric bulk around P, complexes 3 – 7 react with B(C 6 F 5 ) 3 to give O‐bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp 2 Zr(μ‐OCHPhPCy 2 )][MeB(C 6 F 5 ) 3 ]} 2 ( 10a ) with chalcone results in 1,4 addition of the Zr + /P FLP, whereas the reaction of {[Cp 2 Zr(μ‐OCHFcPCy 2 )][MeB(C 6 F 5 ) 3 ]} 2 ( 11a ; Fc=(C 5 H 4 )CpFe) with [Pd( η 3 ‐C 3 H 5 )Cl] 2 yields the unique Zr−Fe−Pd trimetallic complex 13a , which has been characterised by XRD analysis.