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The C≡C bond of alkynylsilanes undergoes 1,2-haloboration with 2-halogeno-1,3,2-diselenaborolano-4,5-[1,2-dicarba- closo -dodecaborane(12)], in competition with reversible insertion into one of the B–Se bonds (selenoboration) to afford a seven-membered ring and finally, by elimination of Me 3 Si–X (X = Cl, Br, I), the corresponding  B -alkynyl derivatives. The reactions were monitored by NMR spectroscopy ( 11 B,  13 C,  29 Si and  77 Se NMR). The proposed solution-state structures are also supported by DFT calculations of single molecule geometries and NMR parameters [B3LYP/6-311 + G(d,p) level of theory].

Reactivity of alkynylsilanes towards B -halogeno-1,3,2-diselenaborolanes with an annelated dicarba- closo -dodecaborane(12) unit