Electrophilic substitution of the nido-dicarbaborate anion 7,8-nido-C _2B _9H _(12) - with sulfenyl chlorides

摘要

Sulfenyl chlorides RSCl (R = p-C _6H _4OMe, Ph, p-C _6H _4NO _2, CN or 2-C _5H _4N) react with 7,8-nido-C _2B _9H _(12) ~- with asymmetric substitution on the pentagonal C _2B _3 face to give 9-RS-7,8-nido-C _2B _9H _(11) ~- (R = p-C _6H _4OMe (3), Ph (4), p-C _6H _4NO _2 (5), CN (6)) and the zwitterion 9-(S-2-C _5H _4NH)-7,8-nido-C _2B _9H _(11) (7), respectively, in high yield, while tBuSCl did not react and S _2Cl _2 led to decomposition. Further reaction of 5-7 with iodine gave the corresponding iodo derivatives NMe _4 [9-I-11-RS-7,8-nido-C _2B _9H _(10)] (R = p-C _6H _4NO _2 (8), CN (9)) and the zwitterion 9-I-11-(S-2-C _5H _4NH)-7,8-nido-C _2B _9H _(11) (10), respectively. Compounds 3-10 were fully characterised by ~1H, ~(11)B, ~(11)B{~1H}, ~(13)C{~1H} spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis, 3-7 also by ~(11)B- ~(11)B{~1H} COSY NMR spectroscopy and 8-10 by X-ray structure determination.