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Trivalent Rare‐Earth Metal Amide Complexes as Catalysts for the Hydrosilylation of Benzophenone Derivatives with HN(SiHMe 2 ) 2 by Amine‐Exchange Reaction
Author(s) -
Shinohara Koichi,
Tsurugi Hayato,
Anwander Reiner,
Mashima Kazushi
Publication year - 2020
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.202002011
Subject(s) - hydrosilylation , benzophenone , chemistry , diethylenetriamine , catalysis , amide , medicinal chemistry , amine gas treating , moiety , lanthanum , cerium , agostic interaction , lanthanide , metal , polymer chemistry , catalytic cycle , inorganic chemistry , stereochemistry , organic chemistry , ion
Abstract The rare‐earth metal complexes Ln( L 1 )[N(SiHMe 2 ) 2 ](thf) (Ln=La, Ce, Y; L 1 = N , N′′ ‐bis(pentafluorophenyl)diethylenetriamine dianion) were synthesized by treating Ln[N(SiHMe 2 ) 2 ] 3 (thf) 2 with L 1 H 2 . The lanthanum and cerium derivatives are active catalysts for the hydrosilylation of benzophenone derivatives with HN(SiHMe 2 ) 2 . An amine‐exchange reaction was revealed as a key step of the catalytic cycle, in which Ln−Si−H β‐agostic interactions are proposed to promote insertion of the carbonyl moiety into the Si−H bond.