Unusual Closure of the Ten-Vertex Nido Cage via Alkylation: Regiospecific Synthesis of 3-Alkyl Derivatives of closo-1,2-C2B8H10

Alkylation of the [nido-5,6-R12C2B8H9]− anions (where R1 = H and Me) with alkyl halides (RX, where R = primary and secondary alkyls) in boiling tetrahydrofuran (THF) proceeds via unusual H2 elimination, followed by cage closure to give a series of the neutral closo-1,2-R12C2B8H7-3-R derivatives in ∼70–80% yields. In contrast, treatment of the unsubstituted [nido-5,6-C2B8H11]− anion with tert-butyl bromide (t-BuBr) led to the formation of the parent closo-1,2-C2B8H10 in >85% yield. The constitution of all compounds isolated has been confirmed unambiguously by multinuclear (11B, 1H, and 13C) nuclear magnetic resonance measurements and α-shift correlation assessments.