Reaction of L(2)PdCl(2) species (L = PMe(2)Ph or Me(2)S) with Li-2[closo-B10H10] or Li-2[closo-B12H12] at room temperature resulted in neutral L(2)-substituted boranes. The following compounds were isolated chromatographically and characterized by multinuclear NMR spectroscopy : 1,10-(PMe(2)Ph)(2)B10H8 (1), 2,7(8)-(PMe(2)Ph)(2)B10H8 (2) (a mixture of enantiomers), 1,6-(PMe(2)Ph)(2)B10H8 (3), 1,7-(PMe(2)Ph)(2)B12H10 (4), 1,12-(Me(2)S)(2)B12H10 (5), and 1,7-(Me(2)S)(2)B12H10 (6) Compound 2 was characterized by an X-ray diffraction study. Colorless crystals were orthorhombic space group P2(1)2(1)2(1), with a = 8.917(3) Angstrom, b = 9.601(3) Angstrom, c = 26.525(12) Angstrom, and Z = 4. The structure was determined by conventional methods and refined to a final value of R = 0.0591 (1886 reflections), R(w) = 0.0522.