Electrophilic substitution of the nido-dicarbaborate anion 7,8-nido-C 2B 9H 12- with sulfenyl chlorides

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, 11B, 11B{ 1H}, 13C{ 1H} spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis, 3-7 also by 11B- 11B{ 1H} COSY NMR spectroscopy and 8-10 by X-ray structure determination. © 2012 The Royal Society of Chemistry.