16872-09-6Relevant articles and documents
REACTION OF CARBORANYL BORON-CENTERED RADICALS WITH PHOSPHITES AND THE ADDITION OF CARBORANE-CONTAINING AND SOME OTHER PHOSPHORANYL RADICALS TO 3,6-DI-TERT-BUTYL-ORTHO-BENZOQUINONE
Tumanskii, B. L.,Kampel', V. Ts.,Bregadze, V. I.,Bubnov, N. N.,Solodovnikov, S. P.,et al.
, (1986)
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Practical synthesis for decahydrodecaborates
Makhlouf, Joseph M.,Hough, William V.,Hefferan, Gerald T.
, p. 1196 - 1198 (1967)
High-yield synthesis of the decahydrodecaborate(2-) anion was achieved from the thermolysis of tetraethylammonium tetrahydroborate(1-), (C2H5)4NBH4, and tetraethylammonium octahydrotriborate(1-), (C2H5)4NB3H8, at atmospheric pressure and 185°. The thermolysis of tetramethylammonium tetrahydroborate(1-), (CH3)4NBH4, under similar conditions gives only trimethylamine borane, (CH3)3NBH3, and methane, while a near equimolar mixture of [(CH3)4N]2B10H10 and [(CH3)4N]2B12H12 was the major product obtained from pyrolysis of tetramethylammonium octahydrotriborate(1-), (CH3)4NB3H8. Although B10H102- was a major product, complex mixtures of products containing the BH4-, B10H102-, B11H14-, and B12H122- anions were obtained from the 185° pyrolysis of potassium and cesium octahydrotriborates(1-), KB3H8 and CsB3H8, respectively. No evidence was obtained for B9H92- or B11H112- when the pyrolysis temperatures were maintained at 185°.
Reduction of hydroxy-functionalised carbaboranyl carboxylic acids to tertiary alcohols by organolithium reagents
Neumann, Wilma,Hiller, Markus,Loennecke, Peter,Hey-Hawkins, Evamarie
, p. 4935 - 4937 (2014)
Reduction of hydroxy-functionalised carbaboranyl carboxylic acids by organolithium reagents yields the corresponding tertiary alcohols. This is in contrast to exo-polyhedral C-C bond cleavage of unsubstituted carbaboranyl carboxylic acids upon reaction with lithium organyls. The proposed dimeric contact ion pairs may also explain the formation of tertiary alcohols instead of the expected ketones.
Access to carbaboranyl glycophosphonates - An odyssey
Stadlbauer, Sven,Welzel, Peter,Hey-Hawkins, Evamarie
, p. 5005 - 5010 (2009)
Novel bis-phosphonate derivatives of carbaboranes, which might be potential boron-delivery agents for boron neutron capture therapy, are described. Conceivable synthetic routes which failed to give the desired compounds are discussed, and finally, a highl
Usyatinskii, A. Ya.,Todres, Z. V.,Shcherbina, T. M.,Bregadze, V. I.,Godovikov, N. N.
, (1983)
Reduction of hydroxy-functionalised carbaboranyl carboxylic acids and ketones by organolithium reagents
Neumann,Hiller,Sárosi,L?nnecke,Hey-Hawkins
, p. 6638 - 6644 (2015)
While the reaction of carbaboranyl carboxylic acids and ketones with organolithium reagents generally leads to cleavage of the exo-polyhedral C-C bond, introduction of a hydroxyl group at the second carbon atom of the cluster enables the reduction of the carbonyl compounds to tertiary alcohols. The proposed mechanism involving the formation of dimeric contact ion pairs was supported by X-ray crystallography and theoretical calculations. This journal is
Marshall et al.
, p. 3361 (1967)
Colquhoun, Howard M.,Greenhough, Trevor J.,Wallbridge, Malcolm G. H.
, (1978)
Preparation and Properties of Inclusion Complexes of 1,2-Dicarbadodecaborane(12) with Cyclodextrins
Harada, Akira,Takahashi, Shigetoshi
, p. 1352 - 1353 (1988)
One-to-one inclusion complexes were obtained in a crystalline state in high yields by treatment of β- and γ-cyclodextrin with 1,2-dicarbadodecaborane(12) (o-carborane), whereas α-cyclodextrin formed a 2:1 (cyclodextrin: guest) complex on sonication, and a 1:1 complex on crystallization from water-propan-2-ol.
Metal-Free Oxidative B?N Coupling of nido-Carborane with N-Heterocycles
Yang, Zhongming,Zhao, Weijia,Liu, Wei,Wei, Xing,Chen, Meng,Zhang, Xiao,Zhang, Xiaolei,Liang, Yong,Lu, Changsheng,Yan, Hong
supporting information, p. 11886 - 11892 (2019/07/18)
A general method for the oxidative substitution of nido-carborane (7,8-C2B9H12?) with N-heterocycles has been developed by using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as an oxidant. This metal-free B?N coupling strategy, in both inter- and intramolecular fashions, gave rise to a wide array of charge-compensated, boron-substituted nido-carboranes in high yields (up to 97 %) with excellent functional-group tolerance under mild reaction conditions. The reaction mechanism was investigated by density-functional theory (DFT) calculations. A successive single-electron transfer (SET), B?H hydrogen-atom transfer (HAT), and nucleophilic attack pathway is proposed. This method provides a new approach to nitrogen-containing carboranes with potential applications in medicine and materials.
Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solid-state investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11
Ba?e, Tomá?,Machá?ek, Jan,Hájková, Zuzana,Langecker, Jens,Kennedy, John D.,Carr, Michael J.
, p. 132 - 140 (2015/12/18)
At 300-500 °C, three C-thiolated closo-dicarbadodecaborane isomers 1-(HS)-1,2-C2B10H11 (1-o), 1-(HS)-1,7-C2B10H11 (1-m), and 1-(HS)-1,12-C2B10H11 (1-p), and two B-thiolated isomers 9-(HS)-1,7-C2B10H11 (9-m) and 9-(HS)-1,2-C2B10H11 (9-o) show two types of reaction: first, removal of an SH group from the closo-dicarbadodecaborane skeleton, and second, skeletal isomerizations from ortho to meta to para that lead to new isomers. A previously unreported SH skip from carbon-to-boron is also observed. The effect of the thiol group on the skeletal rearrangement is discussed. The isomerisation products are assigned on the basis of correlation of their computationally obtained dipole moments with their gas-chromatographic retention times. Computational results on molecular energies for the mono-thiolated species show good agreement between the calculated relative stabilities and the incidence and relative quantities of the isomerization products. Two of the starting B-thiolated isomers, 9-o and 9-m, were characterized using single-crystal X-ray diffraction analyses and their crystallographic packings as well as some selected structural parameters are discussed. All starting compounds were characterized using multinuclear NMR spectroscopy.
