216
7 C–C Bond Formation via Carbocations in the Methane …
14. Olah GA, Lukas J (1967) Stable carbonium ions. XXXIX. Formation of alkylcarbonium
ions via hydride ion abstraction from alkanes in fluorosulfonic acid-antimony pentafluoride
solution. Isolation of some crystalline alkylcarbonium ion salts. J Am Chem Soc 89:2227–
2228
15. Olah GA, Lukas J (1967) Stable carbonium ions. XLVII. Alkylcarbonium ion formation from
alkanes via hydride (alkide) ion abstraction in fluorosulfonic acid-antimony pentafluoridesulfuryl chlorofluoride solution. J Am Chem Soc 89:4739–4744
16. Olah GA, Klopman G, Schlosberg RH (1969) Chemistry in super acids. III. Protonation of
alkanes and the intermediacy of alkanonium ions, pentacoordinated carbon cation of the CH 5
+
type, hydrogen exchange, protolytic cleavage, hydrogen abstraction, and polycondensation of
methane, ethane, 2,2-dimetylpropane and 2,3,3,3-tetramethylbutane in FSO 3 H-SbF 5 . J Am
Chem Soc 91:3261–3268
17. Olah GA, Halpern Y, Shen J, Mo YK (1971) Electrophilic reactions at single bonds. III. H-D
exchange and protolysis (deuterolysis) of alkanes with superacids. The mechanism of acidcatalyzed hydrocarbon transformation reactions involving the σ electron pair donor ability of
single bonds via three-center bond formation. J Am Chem Soc 93:1251–1256
18. Olah GA, Halpern Y, Shen J, Mo YK (1973) Electrophilic reactions at single bonds. XII.
Hydrogen-deuterium exchange, protolysis (deuterolysis), and oligocondensation of alkanes
with superacids. J Am Chem Soc 95:4960–4970
19. Olah GA, DeMember JR, Shen J (1973) Electrophilic reactions at single bonds. X. Hydrogen
transfer, alkylation, and alkylolysis of alkanes with methyl and ethyl fluoroantimonate. J Am
Chem Soc 95:4952–4956
20. White ET, Tang J, Oka T (1999) CH 5
+ : The infrared spectrum observed. Science 284:135–137
21. Kramer GM (1999) CH 5
+ stability and mass spectroscopy. Science 286:1051
22. Hiraoka K, Kebarle P (1975) Energetics, stabilities, and possible structures of CH 5
+ (CH 4 ) n
clusters from gas phase study of equilibria CH 5
+ (CH 4 ) n−1 + CH 4 = CH 5
+ (CH 4 ) n for n =
1–5. J Am Chem Soc 97:4179–4183
23. Tal’roze VL, Ljubimova AK (1999) Secondary processes in the ion source of a mass spectrometer (presented by academician N. N. Semenov 27 VIII (1952)—reprinted from report of
the Soviet Academy of Science volume LXXXVI-n5 (1952). J Mass Spectrom 33:502–504
24. Ahlberg P, Karlsson A, Goeppert A, Lill SON, Dinér P, Sommer J (2001) Solvated CH 5
+ in
liquid superacid. Chem—Eur J 7:1936–1943
25. Boo DW, Lee YT (1993) Infrared spectra of CH 5
+ core in CH 5
+ (H 2 ). Chem Phys Lett
211:358–363
26. Marx D, Parrinello M (1995) Structure quantum effects and three-centre two-electron bonding
in CH 5
+ . Nature 375:216–218
27. Esser A, Forbert H, Marx D (2018) Tagging effects on the mid-infrared spectrum of
microsolvated protonated methane. Chem Sci 9:1560–1573
28. Ivanov SD, Asvany O, Witt A, Hugo E, Mathias G, Redlich B, Marx D, Schlemmer S (2010)
Quantum-induced symmetry breaking explains infrared spectra of CH 5
+ isotopologues.
Nature Chem 2:298–302
29. Asvany O, Yamada KMT, Brünken S, Potapov A, Schlemmer S (2015) Experimental groundstate combination differences of CH 5
+ . Science 347:1346–1349
30. Dinér P (2012) Superacid-protonated ionization of alkanes without carbonium ion formation:
a density function theory study. J Phys Chem A 116:9979–9984
31. Olah GA, Olah JA (1971) Electrophilic reactions at single bonds. IV. Hydrogen transfer from,
alkylation of, and alkyloysis of alkanes by alkylcarbenium fluoroantimonates. J Am Chem
Soc 93:1256–1259
32. Haag WO, Dessau RM (1984) Duality of mechanism of acid-catalyzed paraffin cracking. In:
Proceedings of the 8th International Congress on Catalysis, Berlin, vol 2, Dechema, Frankfurt
am Main, pp 305–316
33. Kotrel S, Knözinger H, Gates BC (2000) The Haag-Gessau mechanism of protolytic cracking
of alkanes. Microporous Mesoporous Mater 35–36:11–20
7 C–C Bond Formation via Carbocations in the Methane …
14. Olah GA, Lukas J (1967) Stable carbonium ions. XXXIX. Formation of alkylcarbonium
ions via hydride ion abstraction from alkanes in fluorosulfonic acid-antimony pentafluoride
solution. Isolation of some crystalline alkylcarbonium ion salts. J Am Chem Soc 89:2227–
2228
15. Olah GA, Lukas J (1967) Stable carbonium ions. XLVII. Alkylcarbonium ion formation from
alkanes via hydride (alkide) ion abstraction in fluorosulfonic acid-antimony pentafluoridesulfuryl chlorofluoride solution. J Am Chem Soc 89:4739–4744
16. Olah GA, Klopman G, Schlosberg RH (1969) Chemistry in super acids. III. Protonation of
alkanes and the intermediacy of alkanonium ions, pentacoordinated carbon cation of the CH 5
+
type, hydrogen exchange, protolytic cleavage, hydrogen abstraction, and polycondensation of
methane, ethane, 2,2-dimetylpropane and 2,3,3,3-tetramethylbutane in FSO 3 H-SbF 5 . J Am
Chem Soc 91:3261–3268
17. Olah GA, Halpern Y, Shen J, Mo YK (1971) Electrophilic reactions at single bonds. III. H-D
exchange and protolysis (deuterolysis) of alkanes with superacids. The mechanism of acidcatalyzed hydrocarbon transformation reactions involving the σ electron pair donor ability of
single bonds via three-center bond formation. J Am Chem Soc 93:1251–1256
18. Olah GA, Halpern Y, Shen J, Mo YK (1973) Electrophilic reactions at single bonds. XII.
Hydrogen-deuterium exchange, protolysis (deuterolysis), and oligocondensation of alkanes
with superacids. J Am Chem Soc 95:4960–4970
19. Olah GA, DeMember JR, Shen J (1973) Electrophilic reactions at single bonds. X. Hydrogen
transfer, alkylation, and alkylolysis of alkanes with methyl and ethyl fluoroantimonate. J Am
Chem Soc 95:4952–4956
20. White ET, Tang J, Oka T (1999) CH 5
+ : The infrared spectrum observed. Science 284:135–137
21. Kramer GM (1999) CH 5
+ stability and mass spectroscopy. Science 286:1051
22. Hiraoka K, Kebarle P (1975) Energetics, stabilities, and possible structures of CH 5
+ (CH 4 ) n
clusters from gas phase study of equilibria CH 5
+ (CH 4 ) n−1 + CH 4 = CH 5
+ (CH 4 ) n for n =
1–5. J Am Chem Soc 97:4179–4183
23. Tal’roze VL, Ljubimova AK (1999) Secondary processes in the ion source of a mass spectrometer (presented by academician N. N. Semenov 27 VIII (1952)—reprinted from report of
the Soviet Academy of Science volume LXXXVI-n5 (1952). J Mass Spectrom 33:502–504
24. Ahlberg P, Karlsson A, Goeppert A, Lill SON, Dinér P, Sommer J (2001) Solvated CH 5
+ in
liquid superacid. Chem—Eur J 7:1936–1943
25. Boo DW, Lee YT (1993) Infrared spectra of CH 5
+ core in CH 5
+ (H 2 ). Chem Phys Lett
211:358–363
26. Marx D, Parrinello M (1995) Structure quantum effects and three-centre two-electron bonding
in CH 5
+ . Nature 375:216–218
27. Esser A, Forbert H, Marx D (2018) Tagging effects on the mid-infrared spectrum of
microsolvated protonated methane. Chem Sci 9:1560–1573
28. Ivanov SD, Asvany O, Witt A, Hugo E, Mathias G, Redlich B, Marx D, Schlemmer S (2010)
Quantum-induced symmetry breaking explains infrared spectra of CH 5
+ isotopologues.
Nature Chem 2:298–302
29. Asvany O, Yamada KMT, Brünken S, Potapov A, Schlemmer S (2015) Experimental groundstate combination differences of CH 5
+ . Science 347:1346–1349
30. Dinér P (2012) Superacid-protonated ionization of alkanes without carbonium ion formation:
a density function theory study. J Phys Chem A 116:9979–9984
31. Olah GA, Olah JA (1971) Electrophilic reactions at single bonds. IV. Hydrogen transfer from,
alkylation of, and alkyloysis of alkanes by alkylcarbenium fluoroantimonates. J Am Chem
Soc 93:1256–1259
32. Haag WO, Dessau RM (1984) Duality of mechanism of acid-catalyzed paraffin cracking. In:
Proceedings of the 8th International Congress on Catalysis, Berlin, vol 2, Dechema, Frankfurt
am Main, pp 305–316
33. Kotrel S, Knözinger H, Gates BC (2000) The Haag-Gessau mechanism of protolytic cracking
of alkanes. Microporous Mesoporous Mater 35–36:11–20