Evidence for an Intermediate in the Methylation of CB11 H12 - with Methyl Triflate: Comparison of Electrophilic Substitution in Cage Boranes and in Arenes
Status PubMed-not-MEDLINE Language English Country Germany Media print-electronic
Document type Journal Article
Grant support
Institute of Organic Chemistry and Biochemistry
61388963
Academy of Sciences of the Czech Republic
CHE-0848477
US National Science Foundation
UV-INV-AE11-41612
Universitat de València
- Keywords
- alkylation, boranes, carboranes, electrophilic substitution, hydrogen scrambling,
- Publication type
- Journal Article MeSH
The trideuteriomethylation of BH vertices in CB11 H12 - and its derivatives with CD3 OTf (OTf=triflate, trifluoromethanesulfonate) yields a mixture of BCD3 and BCHD2 substitution products, thus demonstrating the intermediacy of a species with a long enough lifetime for hydrogen scrambling between the boron vertex and the methyl substituent. No such scrambling is observed if CD3 OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded σ adduct of a methyl cation to the BH bond and the proton scrambling occurs via a transition structure containing a distorted square-pyramidal methane attached axially to a "naked" boron vertex. The subsequent proton or deuteron loss is presently not understood in detail. A general comparison of electrophilic substitution on closo-boranes and arenes is provided and similarities as well as differences are discussed. A recalculation of the optimized geometry of the CB11 Me12 . radical produced a second Jahn-Teller distorted minimum and resulted in a somewhat improved agreement between calculated and measured proton hyperfine coupling constants.
Department de Química Física Universitat de València Dr Moliner 50 46100 Burjassot
Department of Chemistry and Biochemistry University of Colorado Boulder CO 80309 0215
Department of Chemistry Middle East Technical University 06800 Ankara
See more in PubMed
R. N. Grimes, Carboranes, 2nd ed., Academic Press, Oxford, 2011.
C. Douvris, J. Michl, Chem. Rev. 2013, DOI: .
J. Plešek, Z. Plzák, J. Stuchlík, S. Heřmánek, Collect. Czech. Chem. Commun. 1981, 46, 1748-1763.
T. Jelínek, J. Plešek, F. Mareš, S. Heřmánek, B. Štíbr, Polyhedron 1987, 6, 1981-1986.
W. Gu, B. J. McCulloch, J. H. Reibenspies, O. V. Ozerov, Chem. Commun. 2010, 46, 2820-2822.
Z. Xie, C. Tsang, E. T. Sze, Q. Yang, D. T. Chan, T. C. W. Mark, Inorg. Chem. 1998, 37, 6444-6451.
R. R. Srivastava, D. K. Hamlin, S. D. Wilbur, J. Org. Chem. 1996, 61, 9041-9044.
B. T. King, Z. Janoušek, B. Grüner, M. Trammel, B. C. Noll, J. Michl, J. Am. Chem. Soc. 1996, 118, 3313-3314.
B. Grüner, Z. Janoušek, B. King, J. N. Woodford, C. H. Wang, V. Všetečka, J. Michl, J. Am. Chem. Soc. 1999, 121, 3122-3126.
A. B. Yakushev, I. B. Sivaev, K. A. Solntsev, N. T. Kuznetsov, Koord. Khim. 1994, 20, 429;
A. B. Yakushev, I. B. Sivaev, K. A. Solntsev, N. T. Kuznetsov, Chem. Abs. 1994, 121, 220130z.
D. Stasko, C. A. Reed, J. Am. Chem. Soc. 2002, 124, 1148-1149.
Ch.-W. Tsang, Z. Xie, Chem. Commun. 2000, 1839-1840.
W. Jiang, C. B. Knobler, M. D. Mortimer, F. M. Hawthorne, Angew. Chem. 1995, 107, 1470-1473;
Angew. Chem. Int. Ed. Engl. 1995, 34, 1332-1334.
B. T. King, S. Körbe, P. J. Schreiber, J. Clayton, A. Němcová, Z. Havlas, K. Vyakaranam, M. G. Fete, I. Zharov, J. Ceremuga, J. Michl, J. Am. Chem. Soc. 2007, 129, 12960-12980.
L. Lipping, I. Leito, I. Koppel, I. A. Koppel, J. Phys. Chem. A 2009, 113, 12972-12978.
I. A. Koppel, P. Burk, I. Koppel, I. Leito, T. Sonoda, M. Mishima, J. Am. Chem. Soc. 2000, 122, 5114-5124.
J. Kaleta, J. Tarábek, A. Akdag, R. Pohl, J. Michl, Inorg. Chem. 2012, 51, 10819-10824.
J. R. Clayton, B. T. King, I. Zharov, M. G. Fete, V. Volkis, C. Douvris, M. Valášek, J. Michl, Inorg. Synth. 2010, 35, 56-63.
B. L. Booth, R. N. Haszeldine, K. Laali, J. Chem. Soc. Perkin Trans. 1 1980, 2887-2893.
Y. Takano, K. N. Houk, J. Chem. Theory Comput. 2005, 1, 70-77.
A. M. Mebel, K. Najafian, O. P. Charkin, P. R. von Schleyer, J. Mol. Struct. THEOCHEM 1999, 461-462, 187-202.
E. T. White, J. Tang, T. Oka, Science 1999, 284, 135-137.
J. E. Mann, Z. Xie, J. D. Savee, B. J. Braams, J. M. Bowman, R. E. Continetti, J. Am. Chem. Soc. 2008, 130, 3730-3731.
M. G. Fete, Z. Havlas, J. Michl, J. Am. Chem. Soc. 2011, 133, 4123-4131.
N. Rega, M. Cossi, V. Barone, J. Chem. Phys. 1996, 105, 11060-11067.
V. Barone in Recent Advances in Density Functional Methods, Part I (Ed.: D. P. Chong), World Scientific Publ. Co., Singapore, 1996, Chapter 8.
Y. Zhao, D. G. Truhlar, Theor. Chem. Acc. 2008, 120, 215-241.
F. H. Westheimer, Chem. Rev. 1961, 61, 265-273.
M. E. Crestoni, S. Fornarini, J. Am. Chem. Soc. 1994, 116, 5873-5879.
C. A. Reed, K.-Ch. Kim, E. S. Stoyanov, D. Stasko, F. S. Tham, L. J. Mueller, P. D. W. Boyd, J. Am. Chem. Soc. 2003, 125, 1796-1804.
M. L. McKee, M. Bühl, O. P. Charkin, P. R. von Schleyer, Inorg. Chem. 1993, 32, 4549-4554.
M. J. S. Dewar, J. Chem. Soc. 1946, 406-408.
M. J. S. Dewar, J. Chem. Soc. 1946, 777-781.
H. Hirao, T. Ohwada, J. Phys. Chem. A 2003, 107, 2875-2881.
G. Koleva, B. Galabov, J. I. Wu, H. F. Schaefer, P. V. Schleyer, J. Am. Chem. Soc. 2009, 131, 14722-14727.
G. A. Olah, Acc. Chem. Res. 1971, 4, 240-248.
J. Clayden, N. Geeves, S. Warren, Organic Chemistry, 2nd ed., Oxford University Press, Oxford/New York, 2012.
G. W. Wheland, J. Am. Chem. Soc. 1942, 64, 900-908.
G. Koleva, B. Galabov, J. Kong, H. F. Schaefer III, P. R. von Schleyer, J. Am. Chem. Soc. 2011, 133, 19094-19101.
L. Eberson, M. P. Hartshorn, F. Radner in Advances in Carbocation Chemistry, Vol. 2 (Ed.: J. M. Coxon), JAI Press, London, 1995, pp. 207-263.
J. K. Kochi, Adv. Phys. Org. Chem. 1994, 29, 185-272.
L. Eberson, M. P. Hartshorn, F. Radner, O. Persson, J. Chem. Soc. Perkin Trans. 2 1998, 59-70.
A. Pross, Adv. Phys. Org. Chem. 1985, 21, 99-196.
A. Pross, Acc. Chem. Res. 1985, 18, 212-219.
S. S. Shaik, Prog. Phys. Org. Chem. 1985, 15, 197-337.
S. S. Shaik, J. Am. Chem. Soc. 1981, 103, 3692-3701.
J. Kenner, Nature 1945, 156, 369-370.
J. Weiss, Trans. Farraday Soc. 1946, 42, 116-121.
G. A. Benford, C. A. Bunton, E. S. Halberstadt, E. D. Hughes, C. K. Ingold, R. E. Reed, Nature 1945, 156, 688.
C. L. Perrin, J. Am. Chem. Soc. 1977, 99, 5516-5518.
K. Vyakaranam, Z. Havlas, J. Michl, J. Am. Chem. Soc. 2007, 129, 4172-4174.
A. E. Shilov, G. B. Shuĺpin, Chem. Rev. 1997, 97, 2879-2932.
K. M. Waltz, C. N. Muhoro, J. F. Hartwing, Organometallics 1999, 18, 3383-3393.
P. L. Watson, J. Am. Chem. Soc. 1983, 105, 6491-6493.
J. A. Labinger, J. E. Bercaw, Nature 2002, 417, 507-514.
L. Johansson, M. Tilset, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2000, 122, 10846-10855.
Ch. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, Y. Fujiwara, Science 2000, 287, 1992-1995.
B. T. King, B. C. Noll, A. J. McKinley, J. Michl, J. Am. Chem. Soc. 1996, 118, 10902-10903.
A. Wahab, B. Stepp, C. Douvris, M. Valášek, J. Štursa, J. Klíma, M.-C. Piqueras, R. Crespo, J. Ludvik, J. Michl, Inorg. Chem. 2012, 51, 5128-5137.
I. Zharov, Z. Havlas, A. M. Orendt, D. H. Barich, D. M. Grant, M. G. Fete, J. Michl, J. Am. Chem. Soc. 2006, 128, 6089-6100.
V. Volkis, C. Douvris, J. Michl, J. Am. Chem. Soc. 2011, 133, 7801-7809.
J. Plešek, Z. Plzák, J. Stuchlík, S. Heřmánek, Collect. Czech. Chem. Commun. 1981, 46, 1748-1763.
F. Šembera, Z. Janoušek, J. Michl, unpublished results.
Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
M. Valášek, J. Štursa, R. Pohl, J. Michl, Inorg. Chem. 2010, 49, 10247-10254.
Lewis Superacidic Tellurenyl Cation-Induced Electrophilic Activation of an Inert Carborane
Insertion of Carbenes into Deprotonated nido-Undecaborane, B11H13(2-)
