N‐Alkylation of Ammonioundecahydro‐closo‐dodecaborate(1–) for the Preparation of Anions for Ionic Liquids

Abstract

Different N‐alkylated derivatives of ammonioundecahydro‐closo‐dodecaborate(1–), [B12H11NH3]–, were prepared. Strategies for the introduction of one alkyl chain or two equal alkyl chains and the trisubstitution by two different alkyl chains were developed. Several of the resulting salts have low melting points and are examples of a new class of ionic liquids.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

B–N bond formation through palladium-catalyzed, microwave-assisted cross-coupling of nitrogen compounds with iodo-dodecaborate

“…While the chemistry for organocarboranes is well-established, methods for linking the closododecaborates to organic residues are less developed 10 . Heteroatoms such as N, 11 S, 12 and O 13 can be introduced and functionalized further by reactions with nucleophiles [14][15][16][17][18][19] . .…”

Water Structure Recovery in Chaotropic Anion Recognition: High‐Affinity Binding of Dodecaborate Clusters to γ‐Cyclodextrin

“…Borate clusters of the types B 12 X 12 2À and B 12 X 11 Y 2À (X = H, Cl, Br, Ia nd Y = OH, SH, NH 3 + ,N R 3 + ;F igure 1) are poorly coordinating and weakly basic inorganic anions with icosahedral structure and ap ermanent double negative charge of the core. [3] Their discovery in the 1960s led to numerous applications in medicinal chemistry and materials science, [4] among which their use in neutron capture therapy of cancer stands out as apractically relevant one. [5] Thehostguest chemistry of these hydrophilic cluster anions has not been previously described.…”

Boron

“…The phosphine substituted-carborane system, 1,2-(P i Pr 2 ) 2 -closo-1,2-C 2 B 10 H 10 has been used to synthesise copper halide adducts of general formula [Cu 2 (m-X) 2 (1,2-(P i Pr 2 ) 2 -closo-1,2-C 2 B 10 H 10 ) 2 ] (X = Cl, Br, I) which have been fully characterised. 71 The phosphine substituted metallacarboane system (9) and its utility in the formation of exo-polyhedral bound bimetallic systems such as (10) has been described by Stone et al Compound (9) can also be converted to the alkynyl phosphine derivative (11) which upon reaction with [Co 2 (CO) 8 ] is converted to the trimetallic species (12). 72 The complexes (p-cymene)Ru(m-E 2 )Ru(S 2 C 2 B 10 H 10 ) 2 (R 1 CQCR 2 ) (R 1 or R 2 = Ph, H, -Ph-CRCH, Fc), formed by the alkyne addition at the sulfur atoms of two different chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands, have been described and the molecular structures of several products determined.…”

“…9 A new class of low-melting ionic liquids that consist of N,N,N-trialkylammonioundecahydrododecaborate anions, [R 3 N-B 12 H 11 ] À have been reported. 10,11 Hybrid organic-inorganic bis-tetrabutylammonium-7,7 0 -(imiundecahydro-closo-dodecaborate)-9,9 0 -(dihexyl)-2,2 0 -bifluorene (1) has been prepared, and the influence of the closo-dodecaborate cluster on the two-photon absorption properties of bi-fluorene derivatives explored. 12 Computational methods have been used to evaluate the mechanism of the cage opening reaction in the synthesis of the macropolyhedron closo/nido-B 20 H 16 (MeCN) 2 from closo/closo-B 20 H 16 .…”