Donor and ate‐Coordination in Rare‐Earth Metal Bis(dimethylsilyl)amide Complexes

Divalent Transition Metal Silylamide Ate Complexes

“…The X‐ray structure analysis of the donor‐free yttrium complex revealed that interactions between the lithium atoms and adjacent Si–H moieties resulted in a dimeric conformation (see Scheme ). The Si–H vibration in the DRIFT spectrum of 5 is quite broad (Figure 5), which might indicate similar interactions to those in LiY[N(SiHMe 2 ) 2 ] 4 ( O , Scheme ) 31. Naturally, the above‐stated characteristic bands, except that for the Si–H vibration, can also be found in the DRIFT spectra of 1 – 4 (Figure S1).…”

“…To date, {LiY[N(SiHMe 2 ) 2 ] 4 } 2 31 and (thf)LiCe[N(SiHMe 2 ) 2 ] 4 32 are the only structurally characterized ate complexes with bis(dimethylsilyl)amido ligands ( O and P , Scheme ). As yttrium and cerium are trivalent, four silylamido ligands surround the Ln III metal centers.…”

Rare‐Earth Metal Phenyl(trimethylsilyl)amide Complexes

“…[25,26] For example, use of La(OTf) 3 and LiN(SiHMe 2 ) 2 gave complicated product mixtures, while the corresponding reaction with Y(OTf) 3 yielded the tris(amido) derivative Y[N-(SiHMe 2 ) 2 ] 3 (thf) 2 only contaminated with LiOTf [25] and the donor solvent-free ate complex {Y[N(SiHMe 2 ) 2 ] 4 Li} 2 . [26] Use of the bulkier [N(SiMe 3 )(C 6 H 3 iPr 2 -2,6)] ligand might counteract ligand scrambling and allow the isolation of putative complexes Ln[N(SiMe 3 )(C 6 H 3 iPr 2 -2,6)] 2 (OTf)-(thf). However, 1 H NMR spectroscopic investigations of the crude products obtained from the reactions of Ln(OTf) 3 (Ln = Y, Nd) with 2 equiv.…”

Rare‐Earth Metal Bis(dimethylsilyl)amide Complexes Supported by Cyclooctatetraenyl Ligands

“…Compared to [N(SiMe 3 ) 2 -], its sterically less demanding counterpart [N(SiHMe 2 ) 2 -] might provoke new reactivity patterns and structural chemistry. [35][36][37][38][39][40] …”