Emergence of a New [NNN] Pincer Ligand via Si-H Bond Activation and β-Hydride Abstraction at Tetravalent Cerium.

ABSTRACT: The cerium(IV) pyrazolate complexes [Ce(Me₂ pz)₄ ]₂ and [Ce(Me₂ 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(Me₂ pz)₃ (bpsa)] (bpsa=bis((3,5-dimethylpyrazol-1-yl)dimethylsilyl)amido; Me₂ 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(Me₂

SUBMITTER: Werner D 

PROVIDER: S-EPMC7540680 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature