[LiN(SiMe 3 )Ar] 2 ( 1 , Ar = 2,6‐ i Pr 2 C 6 H 3 ) is prepared by the reaction of HN(SiMe 3 )Ar with n BuLi in n ‐hexane. This compound with an unusual structure contains a four‐membered [LiN] 2 heterocycle with two solvent‐free two‐coordinate Li centers. Its molecular structure represents the first solid‐state X‐ray analysis of an uncomplexed [LiN] 2 dimer.
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