The reaction of Li[1-t BuMe 2 Si-1,2-C 2 B 10 H 10 ] with N-(bromoethyl)phthalimide or N-3-(bromopropyl)phthalimide generates unusual carboranyl heterocycles, resulting from nucleophilic substitution followed by insertion of a phthalimide carbonyl into the C-Si bond. The structure of one was determined by single crystal X-ray diffraction.
Reaction of the heterocycles withH 11 ] Ϫ as minor side-products on prolonged reaction. The prolonged reaction of 1b and 1c with hydrazine results in deboronation to give hydrazine solvates of zwitterionic nido-[7-{H 3 N(CH 2 ) n }-7,8-C 2 B 9 H 11 ]. A single crystal X-ray diffraction study for one reveals an elegant dimeric architecture supported by hydrazine-bridged hydrogen bonds. The reaction of the heterocycles with ethanolic KOH results in cluster deboronation and partial deprotection of the amine group to give nido-as potassium salts which can be metathesised to less hygroscopic Me 3 NH ϩ salts. The molecular structure of one of the latter displays hydrogen bonding generating a dimeric unit. Complete deprotection of the amine function in these salts by water-HCl gives zwitterionic aminoalkylcarboranes nido-7-{H 3 N(CH 2 ) n }-7,8-C 2 B 9 H 11 .
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