TY - JOUR
T1 - N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)
AU - Vöge, Andrea
AU - Lork, Enno
AU - Sesalan, Behice Şebnem
AU - Gabel, Detlef
PY - 2009/5/1
Y1 - 2009/5/1
N2 - We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B12H11NH2]2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B12H11N(R1)2C6H5]- (R1 = H, CH3). With 4-(dimethylamino)pyridine, [1-closo-(B12H11NC5H4)-4-N(CH3)2]-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B12H11NHC6H3)-3,4-(CN)2]2- and [1-closo-(B12H11NHC6H2)-2-(NO2)-4,5-(CN)2]2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2-. For [1-closo-B12H11N(CH3)2C6H5]- and [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2- single crystal X-ray structures were obtained.
AB - We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B12H11NH2]2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B12H11N(R1)2C6H5]- (R1 = H, CH3). With 4-(dimethylamino)pyridine, [1-closo-(B12H11NC5H4)-4-N(CH3)2]-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B12H11NHC6H3)-3,4-(CN)2]2- and [1-closo-(B12H11NHC6H2)-2-(NO2)-4,5-(CN)2]2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2-. For [1-closo-B12H11N(CH3)2C6H5]- and [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2- single crystal X-ray structures were obtained.
KW - Aromatic substitution
KW - B-pyridinium
KW - Dodecahydro-closo-dodecaborate
KW - Hofmann elimination
KW - Hydroamination
UR - http://www.scopus.com/inward/record.url?scp=63249132833&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2008.12.053
DO - 10.1016/j.jorganchem.2008.12.053
M3 - Article
AN - SCOPUS:63249132833
SN - 0022-328X
VL - 694
SP - 1698
EP - 1703
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 11
ER -