Rare‐Earth Metal Phenyl(trimethylsilyl)amide Complexes

The reactions of common rare‐earth metal chloride, borohydride, and triflate precursors – LnCl 3 (thf) x , Ln(BH 4 ) 3 (thf) 3 , and La(OTf) 3 – with alkali metal amide complexes M[N(SiMe 3 )(C 6 H 3 i Pr 2 ‐2,6)] (M[NRR′]; M = Li, K) were investigated in thf or hexane as a solvent. A diverse range of products was obtained comprising alkali metal‐free mono(rare‐earth metal) complexes Y[NRR′]Cl 2 (thf) 3 and Ln[NRR′] 2 (BH 4 )(thf) (Ln = Nd, La), as well as the mononeodymium ate complex {Nd[NRR′] 2 (BH 4 ) 2 }{Li(thf) 4 } and polymeric ate complexes {La[NRR′] 2 (thf)(μ‐Cl)K(thf) 2 (μ‐Cl)} n and {Nd[NRR′] 2 (μ‐BH 4 )Li(thf) 2 (μ‐BH 4 )} n . All compounds were characterized by NMR ( 1 H and 13 C) and FTIR spectroscopy, elemental and X‐ray structure analyses. The lithium salts Li[NRR′](thf) 3 and Li 4 (OTf) 4 (thf) 6 were isolated as side products and structurally characterized. The homoleptic complex La[NRR′] 3 was prepared following two synthesis protocols in hexane, either by reacting Ln[NRR′] 2 (BH 4 )(thf) with 1 equiv. of K[NRR′] or treatment of LaCl 3 (thf) 1.25 with 3 equiv. of K[NRR′].