ortho-Carborane

ortho-Carborane is the organoboron compound with the formula C2B10H12. The prefix ortho is derived from ortho. It is the most prominent carborane. This derivative has been considered for a wide range of applications from heat-resistant polymers to medical applications. It is a colorless solid that melts, without decomposition, at 320 °C

Ortho-Carborane

Contaminated orthocarborane
Names
Other names
1,2-Dicarbadodecaborane(12), ortho-dicarbadodecaborane
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.037.164
EC Number
  • 240-897-8
  • InChI=1S/C2B10/c3-1-2-7(1,3)5-9(2,7)10(2)6-8(1,2,10)4(1,3)11(3,5,6)12(5,6,9)10
    Key: DOPDSZSTXZNQMF-UHFFFAOYSA-N
  • [B@@]123B456B178[B@@]49B714B822B337C211B492C131B75=B621
  • [BH]1234[BH]5%12%13[BH]1%10%11[BH]289[BH]367[BH]145[BH]6%14%15[BH]78%16[BH]9%10%17[CH]%11%12%18[CH]1%13%14[BH]%15%16%17%18
Properties
C2H12B10
Molar mass 144.22 g·mol−1
Appearance colorless solid
Melting point 320 °C (608 °F; 593 K)
Hazards
GHS labelling:
Warning
H228, H302, H312, H332
P210, P240, P241, P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P312, P322, P330, P363, P370+P378, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Structure

The cluster has C2v symmetry.[1]

Preparation

Ortho-carborane is prepared by the addition of acetylenes to decaborane(14). Modern syntheses involve two stages, the first involving generation of an adduct of decaborane:[2][3]

B10H14 + 2 SEt2 → B10H12(SEt2)2 + H2

In the second stage, the alkyne is installed as the source of two carbon vertices:[3]

B10H12(SEt2)2 + C2H2 → C2B10H12 + 2 SEt2 + H2

Substituted acetylenes can be employed more conveniently than acetylene gas. For example bis(acetoxymethyl)acetylene adds to the decarborane readily.

B10H12(SEt2)2 + C2(CH2O2CCH3)2 → C2B10H10(CH2O2CCH3)2 + 2 SEt2 + H2

The organic substituents are removed by ester hydrolysis followed by oxidation:[2]

3 C2B10H10(CH2O2CH3)2 + 10 KOH + + 8 KMnO4 → 3 C2B10H12 + 6 CH3CO2K + 8 MnO2 + 6 K2CO3 + 8 H2O

Reactions

Thermal rearrangement

Upon heating to 420 °C, it rearranges to form the meta isomer. The para isomer is produced by heating to temperatures above 600 °C.

Reduction and "reverse isomerization"

ortho-Carborane undergoes 2e- reduction when treated with a solution of lithium in ammonia. The result is the nido cluster 7,9-[C2B10H12]2-. In the dianion, the carbon vertices are not adjacent. The same cluster is produced by reduction of meta-carborane. Oxidation of the resulting 7,9-[C2B10H12]2- gives ortho-carborane.[4]

Deprotonation

Treatment with organolithium reagents gives the dilithio derivative.[5]

C2B10H12 + 2 BuLi → Li2C2B10H10 + 2 BuH

This dilithiated compound reacts with a variety of electrophiles, e.g. chlorophosphines, chlorosilanes, and sulfur.[6]

Base-degradation to dicarbollide
Main article: dicarbollide

Base degradation of ortho carborane gives the anionic 11-vertex derivative, precursor to dicarbollide complexes:[7]

C2B10H12 + NaOEt + 2 EtOH → Na+C2B9H12− + H2 + B(OEt)3
Na+C2B9H12− + NaH → Na2C2B8H11 + H2

Dicarbollides (C2B8H112-) function as ligands for transition metals and f-elements.[8] The dianion forms sandwich compounds, bis(dicarbollides). Dicarbollides, being strong electron donors, stabilize higher oxidation states, e.g. Ni(IV).

Deprotonation of carborane

The CH vertices of closo-dicarbadodecaboranes undergo deprotonation upon treatment with organolithium reagents:[9]

C2B10H12 + 2 BuLi → Li2C2B10H10 + 2 BuH

These dilithiated compounds react with a variety of electrophiles, e.g. chlorophosphines, chlorosilanes, and sulfur.[10] Many of the same compounds can be produced by hydroboration of alkynes:

Li2C2B10H10 + 2 RX → R2C2B10H10 + 2 LiX
L2B10H10 + RC2R → R2C2B10H10 + 2 L (L = MeCN, etc.)

ortho-Carborane can be converted to highly reactive carborynes with the formula B10C2H10.

Substitution at the boron vertices

Unlike the hydrogens on the carbon vertices, the hydrogens on the boron vertices are not acidic and do not react with strong bases. This is because boron is not as electronegative as carbon and thus the polarity of the B—H bonds is relatively low. Substitution at the boron vertices is still possible using halogenating agents through electrophilic substitution or photochemical reactions.[11]

For example, the boron vertices at the 9 and 12 positions opposite to the carbon vertices can be iodinated using iodine and a catalytic amount of AlCl3 while in refluxing dichloromethane.[12]  

Exohedral halogenation leads to an increase in the electron withdrawing effect of the carborane which increases the acidity of the C—H bonds especially when the halogens are located at the 9, and 12 positions.[13] Per-halogenation is also possible and when increasing the number of halide atoms, the π backdonation ability of the halide decreases allowing for the formation of intramolecular halide-halide noncovalent bonds.[14]

Iodinated derivatives of carborane can be further modified to access boron alkylated products via a cross coupling reaction. This can be done by treating the halogenated carborane with a Grignard reagent in the presence of a phosphine palladium complex. The bromo and chloro compounds do not react under the same conditions.[15]

Dimerization of carborane

Upon treatment of ortho-carboranes with organolithium reagents such as n-Butyllithium, the CH vertices of the carborane cage can be deprotonated, affording the dilithiated ortho-carborane cage. Taking advantage of this more active carbon-lithium bond, the metalated carborane cages can then be treated with copper(I) chloride while in organic solvents, resulting in a copper-mediated carbon-carbon coupling reaction of the carborane cages. The copper salt is needed to avoid unwanted carbon-boron and boron-boron coupling reactions. The reaction mixture is allowed to stir at room temperature for two days, forming a copper-metalated carborane cage. Finally, the mixture is treated with 3M hydrochloric acid to quench the reaction process. The crude product is then purified via column chromatography and affords one half-equivalent of the carbon-carbon linked dimer of the original ortho-carborane in high yields. Worth noting is the effect of donating solvents on the yields of the reactions, as yields in solvents such as tetrahydrofuran and diethyl ether afford product in greatly decreased yields.[16]

History

The preparation of closo-dicarbadodecaboranes was reported independently by groups at Olin Corporation and the Reaction Motors Division of Thiokol Chemical Corporation working under the U.S. Air Force and published in 1963. These groups demonstrated the high stability in air of 1,2-closo-dodecaborane and related compounds, presented a general synthesis, described the transformation of substituents without destroying the carborane cluster, and demonstrated the ortho to meta isomerization.[17]

See also

References
  1. Davidson, M. G.; Hibbert, T. G.; Howard, J. A. K.; Mackinnon, A.; Wade, K. (1996). "Definitive crystal structures of ortho-, meta- and para-carboranes: supramolecular structures directed solely by C–H⋯O hydrogen bonding to hmpa (hmpa = hexamethylphosphoramide)". Chem. Commun. (19): 2285–2286. doi:10.1039/CC9960002285.
  2. Charles R. Kutal David A. Owen Lee J. Todd (1968). "closo -1,2-Dicarbadodecaborane(12): [ 1,2-Dicarbaclovododecaborane(12 )]". Inorganic Syntheses. Vol. 11. pp. 19–24. doi:10.1002/9780470132425.ch5. ISBN 978-0-470-13170-1.
  3. M. Frederick Hawthorne; Timothy D. Andrews; Philip M. Garrett; Fred P. Olsen; Marten Reintjes; Fred N. Tebbe; Les F. Warren; Patrick A. Wegner; Donald C. Young (1967). "Icosahedral Carboranes and Intermediates Leading to the Preparation of Carbametallic Boron Hydride Derivatives". Inorganic Syntheses. Vol. 10. pp. 91–118. doi:10.1002/9780470132418.ch17. ISBN 978-0-470-13241-8.
  4. Russell N. Grimes (2016). "10. Icosahedral Carboranes: 1,7-C2B10H12 and 1,12-C2B10H12". Carboranes, 3rd Edition. Elsevier. ISBN 978-0-12-801905-4.
  5. Popescu, A.-R.; Musteti, A. D.; Ferrer-Ugalde, A.; Viñas, C.; Núñez, R.; Teixidor, F. (2012). "Influential Role of Ethereal Solvent on Organolithium Compounds: The Case of Carboranyllithium". Chemistry – A European Journal. 18 (11): 3174–3184. doi:10.1002/chem.201102626. PMID 22334417.
  6. Jin, G.-X. (2004). "Advances in the Chemistry of Organometallic Complexes with 1,2-Dichalcogenolato-o-Carborane Ligands". Coord. Chem. Rev. 248 (7–8): 587–602. doi:10.1016/j.ccr.2004.01.002.
  7. Plešek, J.; Heřmánek, S.; Štíbr, B. (1983). "Potassium dodecahydro-7, 8-dicarba-nido -undecaborate(1-), k[7, 8-c2 b9 h12 ], intermediates, stock solution, and anhydrous salt". Potassium dodecahydro-7,8-dicarba-nido-undecaborate(1-), k[7,8-C2B9H12], intermediates, stock solution, and anhydrous salt. Inorganic Syntheses. Vol. 22. pp. 231–234. doi:10.1002/9780470132531.ch53. ISBN 978-0-470-13253-1.
  8. Hawthorne, M. F.; Young, D. C.; Wegner, P. A. (1965). "Carbametallic Boron Hydride Derivatives. I. Apparent Analogs of Ferrocene and Ferricinium Ion". Journal of the American Chemical Society. 87 (8): 1818–1819. doi:10.1021/ja01086a053.
  9. Popescu, A.-R.; Musteti, A. D.; Ferrer-Ugalde, A.; Viñas, C.; Núñez, R.; Teixidor, F. (2012). "Influential Role of Ethereal Solvent on Organolithium Compounds: The Case of Carboranyllithium". Chemistry – A European Journal. 18 (11): 3174–3184. doi:10.1002/chem.201102626. PMID 22334417.
  10. Jin, G.-X. (2004). "Advances in the Chemistry of Organometallic Complexes with 1,2-Dichalcogenolato-o-Carborane Ligands". Coord. Chem. Rev. 248 (7–8): 587–602. doi:10.1016/j.ccr.2004.01.002.
  11. Grimes, Russell N. (2016). Carboranes (Third ed.). Amsterdam Boston Heidelberg: Elsevier, Academic Press. ISBN 978-0-12-801894-1.
  12. Andrews, John S.; Zayas, Jose; Jones, Maitland (October 1985). "9-Iodo-o-carborane". Inorganic Chemistry. 24 (22): 3715–3716. doi:10.1021/ic00216a053. ISSN 0020-1669.
  13. Sivaev, Igor B.; Anufriev, Sergey A.; Shmalko, Akim V. (March 2023). "How substituents at boron atoms affect the CH-acidity and the electron-withdrawing effect of the ortho-carborane cage: A close look on the 1H NMR spectra". Inorganica Chimica Acta. 547: 121339. doi:10.1016/j.ica.2022.121339.
  14. Poater, Jordi; Escayola, Sílvia; Poater, Albert; Teixidor, Francesc; Ottosson, Henrik; Viñas, Clara; Solà, Miquel (2023-10-18). "Single─Not Double─3D-Aromaticity in an Oxidized Closo Icosahedral Dodecaiodo-Dodecaborate Cluster". Journal of the American Chemical Society. 145 (41): 22527–22538. doi:10.1021/jacs.3c07335. ISSN 0002-7863. PMC 10591335. PMID 37728951.
  15. Li, Ji; Logan, Cameron F.; Jones, Maitland (December 1991). "Simple syntheses and alkylation reactions of 3-iodo-o-carborane and 9,12-diiodo-o-carborane". Inorganic Chemistry. 30 (25): 4866–4868. doi:10.1021/ic00025a037. ISSN 0020-1669.
  16. Ren, Shikuo; Xie, Zuowei (2008-10-13). "A Facile and Practical Synthetic Route to 1,1′-Bis( o -carborane)". Organometallics. 27 (19): 5167–5168. doi:10.1021/om8005323. ISSN 0276-7333.
  17. Heying, T. L.; Ager, J. W.; Clark, S. L.; Mangold, D. J.; Goldstein, H. L.; Hillman, M.; Polak, R. J.; Szymanski, J. W. (1963). "A New Series of Organoboranes. I. Carboranes from the Reaction of Decaborane with Acetylenic Compounds". Inorganic Chemistry. 2 (6): 1089–1092. doi:10.1021/ic50010a002.
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