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Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry
Author(s) -
Walley Jacob E.,
Warring Levi S.,
Wang Guocang,
Dickie Diane A.,
Pan Sudip,
Frenking Gernot,
Gilliard Robert J.
Publication year - 2021
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.202014398
Subject(s) - pnictogen , chemistry , bismuth , carbene , cationic polymerization , ligand (biochemistry) , halide , antimony , crystallography , stereochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , physics , catalysis , biochemistry , superconductivity , receptor , quantum mechanics
We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)‐stabilized bismuth complexes, which feature low‐coordinate cationic bismuth centers with C=Bi multiple‐bond character. Monocations [(CDC)Bi(Ph)Cl][SbF 6 ] ( 8 ) and [(CDC)BiBr 2 (THF) 2 ][SbF 6 ] ( 11 ), dications [(CDC)Bi(Ph)][SbF 6 ] 2 ( 9 ) and [(CDC)BiBr(THF) 3 ][NTf 2 ] 2 ( 12 ), and trication [(CDC) 2 Bi][NTf 2 ] 3 ( 13 ) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl 2 ( 7 ) and (CDC)BiBr 3 ( 10 ). Notably, the dications and trication exhibit C ⇉ Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non‐reductive route to C−Bi π‐bonding character. The CDC‐[Bi] complexes ( 7 – 13 ) were compared with related NHC‐[Bi] complexes ( 1 , 3 – 6 ) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.