title: Electrophilic substitution of the nido-dicarbaborate anion 7,8-nido-C2B9H12- with sulfenyl chlorides.
abstract: Sulfenyl chlorides RSCl (R = p-C(6)H(4)OMe, Ph, p-C(6)H(4)NO(2), CN or 2-C(5)H(4)N) react with 7,8-nido-C(2)B(9)H(12)(-) with asymmetric substitution on the pentagonal C(2)B(3) face to give 9-RS-7,8-nido-C(2)B(9)H(11)(-) (R = p-C(6)H(4)OMe (3), Ph (4), p-C(6)H(4)NO(2) (5), CN (6)) and the zwitterion 9-(S-2-C(5)H(4)NH)-7,8-nido-C(2)B(9)H(11) (7), respectively, in high yield, while tBuSCl did not react and S(2)Cl(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(2)B(9)H(10)] (R = p-C(6)H(4)NO(2) (8), CN (9)) and the zwitterion 9-I-11-(S-2-C(5)H(4)NH)-7,8-nido-C(2)B(9)H(11) (10), respectively. Compounds 3-10 were fully characterised by (1)H, (11)B, (11)B{(1)H}, (13)C{(1)H} spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis, 3-7 also by (11)B-(11)B{(1)H} COSY NMR spectroscopy and 8-10 by X-ray structure determination.
authors.affiliation: Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, 04103 Leipzig, Germany.
authors.forename: René
authors.initials: R
authors.lastname: Frank
authors.forename: Toni
authors.initials: T
authors.lastname: Grell
authors.forename: Markus
authors.initials: M
authors.lastname: Hiller
authors.forename: Evamarie
authors.initials: E
authors.lastname: Hey-Hawkins