Abstract
A series of tris(boratabenzene) lanthanum complexes were synthesized and structurally characterized. Salt elimination of anhydrous LaCl3 with Li[C5H5BR] (R = H, NEt2) provided tris(boratabenzene) lanthanum complexes [C5H5BH]3LaLiCl (1) and [C5H5BNEt2]3LaLiCl(THF) (2) in high yields. Hydroboration of 1-hexene or 3-hexyne with 1 gave the alkyl- or alkenyl-functionalized boratabenzene lanthanum complexes, [C5H5B(CH2)5CH3]3LaLiCl(THF) (3) and [C5H5BC(C2H5)═CH(C2H5)]3LaLiCl(THF) (4), in good yields. Hydroboration of N,N′-diisopropylcarbodiimide with 1 gave the monohydroboration product [C5H5BN(iPr)CHN(iPr)][C5H5BH]2La (5) due to the steric bulk of the [C5H5BN(iPr)CHN(iPr)]− ligand. Complex 5 can undergo further hydroboration with 3-hexyne or dehydrogenative coupling with phenyl acetylene to afford [C5H5BN(iPr)CHN(iPr)][C5H5BC(C2H5)═CH(C2H5)]2La (6) or [C5H5BN(iPr)CHN(iPr)][C5H5BC≡CPh)]2La (7).
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