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

The cerium(IV) pyrazolate complexes [Ce(Me 2 pz) 4 ] 2 and [Ce(Me 2 pz) 4 (thf)] initiate b -hydride abstraction of the bis(dimethylsilyl)amido moiety, to afford 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)), along with other 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.