SYNTHESIS OF ALKYL AND ARYL DERIVATIVES OF CLOSO-B12H122- BY THE PALLADIUM-CATALYZED COUPLING OF CLOSO-B12H11I2- WITH GRIGNARD-REAGENTS

The reaction of [N(n-C4H9)(4)](2)[closo-B12H11I], [N(n-Bu)(4)](2)[2], with Grignard reagents, RMgX, in the presence of catalytic amounts of trans-Pd(PPh3)(2)Cl-2 and CuI in either tetrahydrofuran or 1,4-dioxane solution produced the corresponding alkylated or arylated polyhedral borane anions, closo-B12H11R2-, in good yield. By this method, we have synthesized [N(n-C4H9)(4)](2)[closo-B12H11CH3], [N(n-Bu)(4)](2)[3]; [ N(n-C4H9)(4)](2)[closo-B12P11C6H5], [N(n-Bu)(4)](2)[4]; and Cs-2[closo -B12H11(n-C18H37)], Cs-2[5]. The structures of Cs-2[3] and PPN2[4] hav e been determined by X-ray diffraction studies. Crystallographic data are as follows: for Cs-2[3], orthorhombic, space group Pmcn, a = 954.6 (6) pm, b = 1077.0(7) pm, c = 1396.8(9) pm, Z = 4, R = 0.055; for PPN2 [3], which cocrystallized with two molecules of DMSO and one molecule of toluene, triclinic, space group P (1) over bar, a = 1138.4(10) pm, b = 1920.1(17) pm, c = 2143.2(18) pm, alpha = 93.26(2)degrees, beta = 104.43(2)degrees, gamma = 105.86(2)degrees, Z = 2, R = 0.076.