Synthesis of closo-1,2-H2C2B8Me8 and 1,2-H2C2B8Me7X (X = I and OTf) Dicarbaboranes and Their Rearrangement Reactions.

Methyl-camouflaged dicarbaboranes closo-1,2- and 1,10-H2C2B8Me8 have been prepared in high yields either from nido-5,6-H2C2B8H10 or closo-1,2-H2C2B8H8 via electrophilic methylation reactions and cluster-rearrangement methods. Prepared were also monosubstituted derivatives of general formulation closo-H2C2B8Me7-X (X = I or OTf). The permethylated compounds exhibit extreme air stability in comparison to unprotected counterparts as a consequence of rigid, egg-shaped hydrocarbon structures incorporating inner C2B8 carborane scaffolding. The structures of all compounds isolated were confirmed unambiguously by multinuclear (11B, 1H, 13C, and 19F) NMR measurements, supported by X-ray diffraction analyses and geometry optimization methods on several compounds.