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The most efficient strategies for the synthesis of novel 1,3dichalcogeno-2-phospholanes (chalcogen E = O, S, Se, Te) are introduced, starting from 1,2-dicarba-closo-dodecaborane(12) ("ortho-carborane"), its 1,2-di-lithiated derivative, and various phosphorus halides. The annelation of the phospholane ring with the rigid three-dimensional carborane framework causes markedly different properties when compared with other phospholanes. Most noteworthy are the structural alternatives concerning the orientation of the lone pair of electrons at phosphorus, the instability of Phalides in particular for E = O, and the pronounced tendency for dimerization in the case of P-organo derivatives, which increases from E = Te < Se < S << O. The latter is a consequence of spatial proximity between P-R or electron density at phosphorus and the carborane skeleton. Direct structural evidence is provided for monomers and dimers by single crystal X-ray structural analysis. The solution-state structures follow from consistent sets of multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 31 P, 77 Se, 125 Te NMR). This is complemented by calculations leading to optimized gas-phase geometries at the B3LYP/6-311+G(d,p) level of theory. Most NMR parameters (chemical shifts δ and indirect nuclear spinspin coupling constants n J) are calculated at the same level of theory. These studies indicate that there are cases, for which important features of the solid-state structures may not be retained in solution.

Novel 1,3-dichalcogeno-2-phospholanes with an annelated 1,2-dicarba-closo-dodecaborane(12) Unit