Synthesis and characterization of cyano-substituted carborane-based compounds. Molecular structure of [1-(4-C7H7)-12-(C5H3-3-(CN)-3,4-(CH3)2)-C2B10H10]

Abstract

The reaction of cyanogen chloride with [1-(4-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (7) was found to yield two new C(5)-substituted carborane cluster-based compounds, [1-(4-C(7)H(7))-12-(C(5)H(2)-3-(CN)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (8) and [1-(4-C(7)H(7))-12-(C(5)H-2,4-(CN)(2)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (9). This cyano-substitution pattern is in contrast to the known substitution for the analogous organic quinarene[5.6.7] system. The observed unique cluster-based products may be understood by a combination of steric and electronic effects. Compounds 8 and 9 were characterized by complete multinuclear NMR, (1)H-(1)H COSY NMR, (1)H-(13)C HMQC NMR, FTIR, UV-Vis, IR, MS data and a single crystal analysis for 8 [X-ray data for 8: C(17)H(25)B(10)N, monoclinic, space group P2(1)/n with cell constants a = 8.6794(17) Å, b = 11.021(2) Å, c = 43.175(9) Å, β = 91.00(3)°, V = 4129.2(14) Å(3), Z = 8, R(1) = 0.0729, wR(2) = 0.1464].

Carboranes in the chemist's toolbox

“…63 Among a number of important topics not specifically covered are nonlinear optical materials, [166][167][168][169][170][171][172] liquid crystals, [173][174][175][176][177][178][179] and ionic liquids, 180 among others. I have barely scratched the surface of the burgeoning field of biomedical applications, on which a formidable literature has accumulated.…”

“…I have barely scratched the surface of the burgeoning field of biomedical applications, on which a formidable literature has accumulated. 63 Among a number of important topics not specifically covered are nonlinear optical materials, [166][167][168][169][170][171][172] liquid crystals, [173][174][175][176][177][178][179] and ionic liquids, 180 among others. What should be clear from this discussion is the versatility of carboranes and metallacarboranes as tools that can be applied to a broad range of problems in the laboratory and in the realm of applied technology.…”

Boron, aluminium, gallium, indium and thallium

“…[60][61][62][63] A number of papers have been published in 2011 that report the use of closo-{C 2 B 10 } carborane units in non-linear optic, luminescent or fluorescent complexes. [64][65][66][67][68][69] Carborane units have also been extensively exploited in pharmacological applications with several papers on, and around the topic being published in 2011, [70][71][72] as well a review of the topic. 73 A series of low-melting ammonium salts based on the [nido-7,8-C 2 B 9 H 12 ] À anion have been synthesised and characterised, and their physicochemical properties including spectroscopic properties, thermal properties, surface properties, solubility, density, viscosity, electrochemical properties, and tribological properties have been studied in detail, and reported.…”