The reaction of phenylchlorophosphino-substituted 1,2-dicarba-closo-dodecaboranes(12) with elemental sulfur and molecular structures of rac-1,2-bis(phenylchlorophosphino)-1,2-dicarba-closo-dodecarborane(12) and 1-phenylchlorothiophosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12)

rac-1,2-Bis(phenylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12) (1) r eacts with four equivalents of sulfur at 185-190 degrees C in undecane to g ive the cyclic anhydride of 1,2-bis(phenylthiophosphoryl)-1,2-dicarba-closo -dodecaboranyl(12)-dithiodiphosphinic acid (2). Under comparable conditions , 1-phenyl-chlorophosphino-1,2-dicarba-closo-dodecaborane(12) (4) and 1-phe nylchlorophosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12) (5) react wi th sulfur to give 1-phenylchlorothiophosphino-1,2-dicarba-closo-dodecaboran e(12) (6) and 1-phenylchlorothiophosphino-2-phenyl-1,2-dicarba-closo-dodeca borane(12) (7). Compounds 4-7 were characterized by H-1, P-31, C-13 and B-1 1 NMR spectroscopy and elemental analysis, and X-ray structure determinatio ns were carried out on 1 and 7. (C) 1998 Elsevier Science Ltd. All rights r eserved.