The substitution of dodecaborate with other heteroatoms was described early on (mostly for O, N, and S ), and these atoms have been used to link the cluster to organic moieties. The formation of a direct B-C connection has been limited to very few reactions, and for connecting a larger organic moiety, only cross-coupling reactions (Kumada and Negishi ), and only with Grignard reagents, have been successful (see Scheme 1). This severely limits the chemical space of compounds which can be used, and reduces drastically the possibilities to use the unique properties of dodecaborate. Overcoming this limitation represents a very desired goal, and poses a formidable task.