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Emergence of a New [NNN] Pincer Ligand via Si−H Bond Activation and β‐Hydride Abstraction at Tetravalent Cerium
Author(s) -
Werner Daniel,
Bayer Uwe,
Schädle Dorothea,
Anwander Reiner
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.202000625
Subject(s) - cerium , chemistry , hydride , ligand (biochemistry) , oxidation state , redox , moiety , medicinal chemistry , nucleophile , bond cleavage , stereochemistry , inorganic chemistry , metal , organic chemistry , catalysis , biochemistry , receptor
Abstract The cerium(IV) pyrazolate complexes [Ce(Me 2 pz) 4 ] 2 and [Ce(Me 2 pz) 4 (thf)] initiate β‐hydride abstraction of the bis(dimethylsilyl)amido moiety, to afford a heteroleptic cerium(IV) species containing a dimethylpyrazolyl‐substituted silylamido ligand, namely [Ce(Me 2 pz) 3 (bpsa)] (bpsa=bis((3,5‐dimethylpyrazol‐1‐yl)dimethylsilyl)amido; Me 2 pz =3,5‐dimethylpyrazolato), along with some cerium(III) species. Remarkably, the nucleophilic attack of the pyrazolyl at the silicon atom and concomitant Si−H‐bond cleavage is restricted to the tetravalent cerium oxidation state and appears to proceed via the formation of a transient cerium(IV) hydride, which engages in immediate redox chemistry. When [Ce(Me 2 pz) 4 ] 2 is treated with [Li{N(SiMe 3 ) 2 }], that is, in the absence of the SiH functionality, any redox chemistry did not occur. Instead, the ceric ate complex [LiCe 2 (Me 2 pz) 9 ] and the stable mixed‐ligand ceric species [Ce(Me 2 pz) 2 {N(SiMe 3 ) 2 } 2 ] were obtained.