Bis(imino)carbazolate: A Master Key for Barium Chemistry

Reported here is a readily available bis(imino)carbazole‐based proligand that constitutes a convenient entry point into the challenging synthetic molecular chemistry of barium. It enables the preparation of rare or even, up to now, unknown, solution‐stable heteroleptic barium complexes. The synthese...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-06, Vol.59 (23), p.9120-9126
Main Authors: Chapple, Peter M., Kahlal, Samia, Cartron, Julien, Roisnel, Thierry, Dorcet, Vincent, Cordier, Marie, Saillard, Jean‐Yves, Carpentier, Jean‐François, Sarazin, Yann
Format: Article
Language:English
Subjects:
alkaline-earth metals
Barium
Barium fluorides
Carbazole
Carbazoles
Chemical Sciences
Coordination chemistry
Fluorides
Iodides
ligand design
structure elucidation
X-ray diffraction
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Summary:Reported here is a readily available bis(imino)carbazole‐based proligand that constitutes a convenient entry point into the challenging synthetic molecular chemistry of barium. It enables the preparation of rare or even, up to now, unknown, solution‐stable heteroleptic barium complexes. The syntheses and structural features for the first molecular barium fluoride and the first barium stannylide, with an unsupported Ba−Sn bond, are described, along with other carbazolate barium species: an amide (both a remarkably stable starting material and an excellent hydrophosphination precatalyst), iodide, and silanylide. DFT analysis of bonding patterns in the barium stannylide and barium silanylide highlights a prevailingly ionic barium–tetrelide bond with a small covalent contribution. Barium rocks! A new carbazole‐based ligand, which is readily available on large scale, enables the syntheses of yet unknown solution‐stable barium complexes, for example, barium fluoride and barium stannylide species, which display unusual bonding patterns.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202001439