Abstract
Summary of main observation and conclusionThe reactivity of homoleptic rare‐earth metal aryloxide based Lewis pairs toward organic azide substrates has been investigated herein. Treatment of RE(OAr)3 (RE = La, Sm, Y, and Sc, Ar = 2,6‐tBu2‐C6H3), PEt3 and Me3SiN3 in 2 : 1 : 1 molar ratio resulted in formation of separated ion pair complexes [Me3Si‐PEt3]+[(ArO)3RE‐N=N=N‐RE(OAr)3]– under mild conditions. Replacement of phosphine with the nitrogen‐containing Lewis base 1,4‐diazabicyclo[2.2.2]octane (DABCO) produced analogous rare‐earth azide complexes with [Me3Si‐DABCO]+ counterions. In contrast, reaction of the La(OAr)3/PEt3 Lewis pair with 1‐adamantyl azide (AdN3) afforded the typical frustrated Lewis pair‐type 1,1‐addition product. A tetrahydrofuran ring‐opening reaction was also observed for the resulting rare‐earth azide complex with the [Me3Si‐PEt3]+ cation, with cleavage of the C—O bond by Si/P cooperation.
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