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Heavy Carbene Analogues: Donor‐Free Bismuthenium and Stibenium Ions
Author(s) -
Olaru Marian,
Duvinage Daniel,
Lork Enno,
Mebs Stefan,
Beckmann Jens
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201803160
Subject(s) - aryl , chemistry , valence electron , ion , alkyl , divalent , carbene , valence (chemistry) , crystallography , medicinal chemistry , electron , terphenyl , stereochemistry , main group element , transition metal , organic chemistry , catalysis , physics , quantum mechanics
Kinetically stabilized congeners of carbenes, R 2 C, possessing six valence electrons (four bonding electrons and two non‐bonding electrons) have been restricted to Group 14 elements, R 2 E (E=Si, Ge, Sn, Pb; R=alkyl or aryl) whereas isoelectronic Group 15 cations, divalent species of type [R 2 E] + (E=P, As, Sb, Bi; R=alkyl or aryl), were unknown. Herein, we report the first two examples, namely the bismuthenium ion [(2,6‐Mes 2 C 6 H 3 ) 2 Bi][BAr F 4 ] ( 1 ; Mes=2,4,6‐Me 3 C 6 H 2 , Ar F =3,5‐(CF 3 ) 2 C 6 H 3 ) and the stibenium ion [(2,6‐Mes 2 C 6 H 3 ) 2 Sb][B(C 6 F 5 ) 4 ] ( 2 ), which were obtained by using a combination of bulky meta ‐terphenyl substituents and weakly coordinating anions.