Potential Precursors for Terminal Methylidene Rare‐Earth‐Metal Complexes Supported by a Superbulky Tris(pyrazolyl)borato Ligand

: A series of solvent-free heteroleptic terminal rare-earth-metal alkyl complexes stabilized by a superbulky tris(pyrazolyl)borato ligand with the general formula [TptBu,Me LnMeR] have been synthesized and fully characterized. Treatment of the heterobimetallic mixed methyl/tetramethylaluminate compounds [TptBu,Me LnMe(AlMe4 )] (Ln=Y, Lu) with two equivalents of the mild halogenido transfer reagents SiMe3 X (X=Cl, I) gave [TptBu,Me LnX2 ] in high yields. The addition of only one equivalent of SiMe3 Cl to [TptBu,Me LuMe(AlMe4 )] selectively afforded the desired mixed methyl/chloride complex [TptBu,Me LuMeCl]. Further reactivity studies of [TptBu,Me LuMeCl] with LiR or KR (R=CH2 Ph, CH2 SiMe3 ) through salt metathesis led to the monomeric mixed-alkyl derivatives [TptBu,Me LuMe(CH2 SiMe3 )] and [TptBu,Me LuMe(CH2 Ph)], respectively, in good yields. The SiMe4 elimination protocols were also applicable when using SiMe3 X featuring more weakly coordinating moieties (here X=OTf, NTf2 ). X-ray structure analyses of this diverse set of new [TptBu,Me LnMeR/X] compounds were performed to reveal any electronic and steric effects of the varying monoanionic ligands R and X, including exact cone-angle calculations of the tridentate tris(pyrazolyl)borato ligand. Deeper insights into the reactivity of these potential precursors for terminal alkylidene rare-earth-metal complexes were gained through NMR spectroscopic studies.