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Unexpected Selective Methyl Group Abstractions from SiMe 3 Moieties of CH 2 SiMe 3 Ligands To Give New Cationic Titanium Complexes
Author(s) -
Fischer Malte,
Barbul Daniel,
Schmidtmann Marc,
Beckhaus Ruediger
Publication year - 2019
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.201900599
Subject(s) - chemistry , cationic polymerization , ligand (biochemistry) , titanium , nitrile , medicinal chemistry , lewis acids and bases , lone pair , methyl group , chelation , stereochemistry , alkylation , betaine , group (periodic table) , polymer chemistry , inorganic chemistry , molecule , organic chemistry , catalysis , biochemistry , receptor
The synthesis of the alkylated pentafulvene titanium complex Cp*Ti(CH 2 SiMe 3 )(π‐η 5 :σ‐η 1 ‐C 5 H 4 =CR 2 ) (CR 2 =adamantylidene) is described. The coordination mode of the pentafulvene ligand in this complex allowed for the subsequent synthesis of a series of nitrile‐insertion products. By reacting these neutral compounds with the strong Lewis acid B(C 6 F 5 ) 3 , unprecedented selective methyl‐group abstractions from the SiMe 3 moieties under formation of novel cationic titanium complexes with the corresponding MeB(C 6 F 5 ) 3 − anion are demonstrated. The proposed silylium ion intermediates of these reactions are directly stabilized by either the exocyclic carbon atom of the pentafulvene ligand or by the lone pairs of the nitrogen atoms of the chelating Cp,N‐ligands. In addition, a titanium enamine complex and its reaction with B(C 6 F 5 ) 3 is reported, which results in the formation of a betaine.