Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 53, Pages 12194-12205Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202000625
Keywords
cerium; hydride abstraction; lithium; pincer ligands; silicon
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Funding
- Projekt DEAL
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The cerium(IV) pyrazolate complexes [Ce(Me(2)pz)(4)](2)and [Ce(Me(2)pz)(4)(thf)] initiate beta-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(SiMe3)(2)}], that is, in the absence of the SiH functionality, any redox chemistry did not occur. Instead, the ceric ate complex [LiCe2(Me(2)pz)(9)] and the stable mixed-ligand ceric species [Ce(Me(2)pz)(2){N(SiMe3)(2)}(2)] were obtained.
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