Non Classical Carbocations

Nonclassical Carbocations
H
C
From Controversy to Convention
H
H
A Stoltz Group Literature Meeting

brought to you by
Chris Gilmore
June 26, 2006
8 PM
147 Noyes
Outline
1. Introduction
2. The Nonclassical Carbocation Controversy
- Winstein, Brown, and the Great Debate
- George Olah and ending the discussion
- Important nonclassical carbocations
3. The Nature of the Nonclassical Carbocation
- The 3-center, 2-electron bond
- Cleaving C-C and C-H bonds
- Intermediate or Transition state? Changing the way we think about carbocations
4. Carbocations, nonclassical intermediates, and synthetic chemistry
- Biosynthetic Pathways
- Steroids, by W.S. Johnson
- Corey's foray into carbocationic cascades
- Interesting rearrangements
- Overman and the Prins-Pinacol
Carbocations: An Introduction
Traditional carbocation is a low-valent, trisubstituted electron-deficient carbon center:
R
LG
superacid
R
R
RR
R
R
"carbenium
ion"
LGH
- 6 valence e- planar structure

- empty p orbital
Modes of stabilization:
Heteroatomic Assistance
-bond Resonance
-bond Participation
R
H2C
X
Lone Pair
Resonance
Anchimeric
Assistance
Allylic
Stabilization
Homoconjugation
Hyperconjugation
Non-Classical
Interaction
Outline
1. Introduction
The Nonclassical Problem: Early Curiosities

Wagner, 1899:
1,2 shift
OH
H
- H+
Meerwein, 1922:
1,2 shift
OH
Meerwin, H. Chem. Ber. 1922, 55B, 2500.

Ruzicka, 1918:
Nuc
Nuc
OH
Nuc
Ruzicka, L. Helv. Chim. Acta, 1918, 1, 110.
The Nonclassical Problem: An Indecent Proposal

Winstein and Trifan, 1949
Rates of solvolysis
aqueous solvent
aqueous solvent
OBs
350
O
O S
Br
O
= OBs
Winstein, Trifan. J. Am. Chem. Soc., 1949, 71, 2953.
OBs

Rates of solvolysis
aqueous solvent
aqueous solvent
OBs
350
OBs
Enantiomerically pure starting material...

7
7
3
5
2
Acetone, H2O
OBs
OAc
5
6 1
KOAc
3
OAc
3
O
O S
Br
AcO
4 5
2
1
= OBs
1
OAc
1:1 Mixture of enantiomers

Rates of solvolysis
aqueous solvent
aqueous solvent
OBs
350
Enantiomerically pure starting material...
7
OBs
5
6
2
1
7
Acetone, H2O
OBs
OAc
KOAc
Br
O
= OBs
3
OAc
O
O S
5
6 1
AcO
4 5
2
1
2
1
OAc
1:1 Mixture of enantiomers
HOAc
OBs
OAc
OAc
aqueous solvent
aqueous solvent
OBs
350
OBs
HOAc
OBs
OAc
OAc
aqueous solvent
aqueous solvent
OBs
350
OBs
"It is attractive to account for these results by way of the bridged (nonclassical) formulation
for the norbornyl cation involving accelerated rate of formation from the exo precursor by
anchimeric assistance." -Saul Winstein
HOAc
OBs
OAc
OAc
aqueous solvent
aqueous solvent
OBs
350
OBs
"It is attractive to account for these results by way of the bridged (nonclassical) formulation
for the norbornyl cation involving accelerated rate of formation from the exo precursor by
anchimeric assistance." -Saul Winstein
The Response of the Traditionalists- H. C. Brown

Strain release improves exo to endo ratio:
OBs
OBs
OBs
PNB
350
Exo/Endo
13
78
Not only must strain have some impact, but direct ionization
hinders rate of solvolysis of endo norbornyl system.
endo
exo
LG
LG
Solvolysis proceeds through unassisted ionization:

- relief of strain accelerates endo ionization
- steric effects hinder ionization of endo isomer
- exo is not fast, endo is slow
Brown, H.C. J. Am. Chem. Soc. 1964, 86, 1248-1250.
A Bonding Experience- Brown's Challenge

Brown insisted upon two stable, equilibrating classical carbocaitonic forms for the norbornyl cation:
"The norbornyl cation does not possess sufficient electrons

to provide a pair for all of the bonds required by the
proposed bridged structures. One must propose a new
bonding concept, not yet established in carbon structures."
- H. C. Brown, 1965


- H. C. Brown, 1965
So, if not classical carbenium ions, what must nonclassical carbocations be?
R
R
R
- a pentavalent carbon
- distinct 3-center, 2-electron bond
- 8 valence e- between 6 atoms
means electron-poor carbon
"carbonium ion"
Brown, H. C. J. Am. Chem. Soc. 1965, 87, 2137-2153.
P.D. Bartlett, Nonclassical Ions, W.A. Benjamin, New York, 1965.


- H. C. Brown, 1965
So, if not classical carbenium ions, what must nonclassical carbocations be?
H
B
isoelectronic
B
H
- a pentavalent carbon
- distinct 3-center, 2-electron bond
- 8 valence e- between 6 atoms
means electron-poor carbon
Contain too few electrons to allow a pair for each "bond"; must have delocalized electrons
P.D. Bartlett, Nonclassical Ions, W.A. Benjamin, New York, 1965.
Enter George Olah

- Previous work with isolable carbocations possible because of superacids
and stable ion media.
- Isolated the first stable carbocation in 1964 and was able to characterize with 13C NMR
Me
SbF5
Me
13C
Me
Me
Me
Me
shift was 300 ppm

downfield from SM!
(335.2 ppm)
SbF6
J. Am Chem. Soc. 1964, 86, 1360
- Superacids designed to prevent proton elimination to quench carbocations
H
Me
Me
Me
Me
- pKa's are measured anhydrously by Hammet acidiy function Ho

Ho
anhydrous sulfuric acid
-11.9
perchloric acid
-13.0
Superacids can reach acidities of Ho= -28, or 1016 times acidity of
triflic acid
-14.1
anhydrous sulfuric acid.
magic acid (FSO3HSbF5)
-21.0
Proving the Existence of the Carbonium Ion

1H
NMR Studies of Olah, Saunders and Schleyer
SbF5
F
6,2 shift
25 C
7
W-M
SbF5, SO2
-60 to -120C
Broad singlet corresponds

to fast Wagner-Meerwein
and hydride shifts, -3.75
-3.1 ppm
3
6
3,2 shift
Resolves 3 singlets, 4:1:6

at -5.35, -3.15, -2.20 ppm
Shows 2-norbornyl ion stable
in solution as equilibrating
Wagner-Meerwein shifts OR
mesomeric intermediate
Saunders, M.; Schleyer, P.; Olah, G. A. J. Am. Chem. Soc. 1964, 86, 5680.

1H
NMR Studies of Olah, Saunders and Schleyer
SbF5
F
6,2 shift
3,2 shift
25 C
7
W-M
3
6
-60 to -120C
H
H
H
H
H
H
H
H
SbF5, SO2
Broad singlet corresponds

to fast Wagner-Meerwein
and hydride shifts, -3.75
-3.1 ppm
H
H
H
H
H
H
H
H
4 (-5.35 ppm)
1 (-3.15 ppm)
6 (-2.20 ppm)
Saunders, M.; Schleyer, P.; Olah, G. A. J. Am. Chem. Soc. 1964, 86, 5680.

1H
spectra at low temps
5
6
1,2,6
3,5,7
2
1
A
SbF5, SO2
-100 C
3,5
1,2
6 4
7
B
SbF5, SO2
F
-157 C
Olah, G. A. J. Am. Chem. Soc. 1982, 104, 7105.

7
13C
spectra at low temps
5
6
1,2,6
3,5,7
2
1
A
SbF5, SO2
-80 C
1,2
B
3,5
7,6
SbF5, SO2
F
-158 C
Olah, G. A. J. Am. Chem. Soc. 1982, 104, 7105.

Core Electron Spectroscopy for Chemical Analysis (ESCA)
- Exploits photoelectric effect to measure ion affinity for electrons.
- Trivalent classical carbocation shows charge localization on 1 atom increases e- binding energy by ~5eV
- Timescale is ~ 1018 Hz, much faster than NMR and Wagner-Meerwein shifts
eV
Me
Me
Me
eV = 3.4
eV = 4.2 - 4.3
H
eV = 3.7
eV
Me
Olah, G. A.; Mateescu, L. A. J. Am. Chem. Soc. 1970, 92, 7231.


Core Electron Spectroscopy for Chemical Analysis (ESCA)
- Exploits photoelectric effect to measure ion affinity for electrons.
- Trivalent classical carbocation shows charge localization on 1 atom increases e- binding energy by ~5eV
- Timescale is ~ 1018 Hz, much faster than NMR and Wagner-Meerwein shifts
eV
Me
Me
Me
eV = 3.4
eV = 4.2 - 4.3
H
eV
Me
eV = 1.7

Closing the Debate

7
3
5
6
vs.
Solid-state 13C NMR studies at 5 K
Isolated crystals allowed x-ray determination of

ion's structure:
Me
Me
Calculations reveal
that Wagner-Meerwein
shifts would require a
barrier of 0.2 kcal/mol
and occur at 105 Hz to
avoid resolution at 5 K,
setting migration equal
to a vibrational transition
Me
1.739
1.442
2.092
1.467
Me
Laube, T. Angew. Chem. Int. Ed. Engl. 1987, 26, 560
For an excellent review of the nonclassical ion

controversy:
- Olah, G. A.; Prakash, G. K. S.; Saunders, M. Acc. Chem.
Res. 1983, 16, 440-449.
- Olah, G. A. Angew. Chem. Int. Ed. Engl. 1995, 34, 13931405
Yannoni, C. S.; Myhre, P. C. J. Am. Chem. Soc. 1982, 104, 7381-7383
Other Important Nonclassical Carbocations

H
H
C
H
H
methonium
H
H
H
- Parent for all nonclassical carbocations.

- 8 Valence electrons rendered deficient by electron pair
sharing between 3 atoms
H
trigonal
bipyramidal
Geometry:
Cs
H
H
- initially suggested trigonal bipyramidal structure

- Ab initio calculations postulated Cs symmetry (as shown)
- Low bond-bond proton migration barriers lend to completely
delocalized theory of bonding
H
C
H
H
delocalized
H
H
H
H
H
H
HH
HH
H+
H H
protonolysis
H+
H2
HH
H
H
C
H
H
H
H
H
Olah, G. A.; Klopman, G. J. Am. Chem. Soc. 1969, 91, 3261
H
C

H
H
C
H
cyclopropylcarbinyl
OH
Studies by Roberts in 1951:
Cl
48%
EtOH,
H2O
OH
47%
unsymmetrical
stabilization
5%
OH
Roberts, J.D.; et. al. J. Am. Che. Soc. 1951, 73, 3542.

H
H
C
H
cyclopropylcarbinyl
OH
Studies by Roberts in 1951:
Cl
48%
EtOH,
H2O
OH
47%
unsymmetrical
stabilization
5%
Schleyer's Solvolytic Studies and Structural Revision in 1966:

OH
Me
Me
Me
Me
Me
Me
OH
DNB
krel = 1
DNB
krel = 11
Me
krel = 82
Me
krel = 490
Me
Me
DNB
DNB
Me
Me
OH
OH
OH
R R
R R
symmetrical stabilization
Schleyer, P. v. R. J. Am. Chem. Soc. 1966, 88, 2321.

H
H
C
H
7-norbornenyl
Solvolytic studies by Winstein (JACS 1956, 78, 592)

TsO
AcO
HOAc
k2/k1 = 1011
k1
AcO
TsO
HOAc
k2
Norbornene Solvolysis
occurs with complete
retention of stereochemistry!

H
H
C
H
7-norbornenyl
Solvolytic studies by Winstein (JACS 1956, 78, 592)

AcO
TsO
HOAc
k2/k1 = 1011
k1
AcO
TsO
HOAc
k2
1H
Norbornene Solvolysis
occurs with complete
retention of stereochemistry!
NMR study of norbornadienyl model system proved nonequivalence of protons in norbornenyl cation
2,3 @ 2.54 ppm, 5,6 @ 3.90 ppm
5
6
3
2
Winstein, S.; Brookhart, M. J. Am. Chem. Soc. 1972, 94, 2347.

H
H
C
H
phenonium ion
Aromatic group participation

Walden Inversion:
Ph
Ph
HOAc
OTs
Ph
OAc
OAc
1
racemization
Me
Me
H
Me
Me
H
H
H
Cram, D. D. J. Am. Chem. Soc. 1949, 71, 3183

H
H
C
H
cyclopropyl
assistance
Properties of Cyclopropane are similar to an olefin:

H
H
C
Problem solved by solvolysis

OBs
HOAc
OBs
cyclopropyl
assistance
OAc
krel
1
OAc
HOAc
OBs
1014
OAc
HOAc
0.333
BsO
HOAc
OAc
5
Tsuji, et. al. J. Am. Chem. Soc. 1967, 89, 1953.; Wells, et. al. Tetrahedron, 1966, 22, 2007.
Outline
1. Introduction
The 3-Center, 2-electron Bond

Diborane and the stable 3-center 2-electron bond.
H
H
B
H
H
H
H
H
H
B
H
H
BR3
- Borane dimers consist of two 3-center 2-electron bonds

- Delocalized electron-poor region at center of dimer
R2B
Electon-poor carbon analogs: -bond donors

Postulated first by DeWar in 1945 as -complex
Cationic complexes and MO theory
E+
E+
E+
E+
R2C
CR2
R2C
CR2
Protonating an Alkane
Much less nucleophilic than -bonds, C-C and C-H bonds donate as well:
Me3C
HF-SbF5
CH3
H+
Me3C
H
CH2
Me3C
CH4
H
Me3C
CH2
CH3
Me
Me
Me
Calculated Protonolysis Activation

Barriers (Sb2F11.HF2 @ 298K)
Ho (kcal/mol)
Alkane
CH4
21.0
C2H6
19.3
19.3
Calculated C-C Cracking Activation

Barriers (Sb2F11.HF2 @ 298K)
H2
Me3C
H
H
Alkane
C2H6
35.0
C3H8
30.0
18.7
Ho (kcal/mol)
19.9
18.3
Mota, et. al. J. Phys. Chem. B 2001, 105, 4331.

Ramsden Tetrahedron 2004, 60, 3293.
Olah, et al. Angew. Chem. Int. Ed. Eng. 1973, 12, 173.
28.7
Protonating an Alkane
Much less nucleophilic than -bonds, C-C and C-H bonds donate as well:
Linear or bridged transition state in protonation?
Olah vs. Hogeveen
A
H H
R
H+
H
R
H
R
B H
Olah, 1971
R
R
D2,
H
R
H+
Me
Me
D2,
Me
H+
H
R
D
R
Olah's general order of alkane bond reactivity:

H
R
H
R
R
>
R3C
CR3
>
R
H
H
R
>
R
H
H
H
Olah, et al. J. Am. Chem. Soc. 1971, 93, 1251.

Hogeveen, et al. Recl. Trav. Chim. Pays-Bas. 1969, 88, 703.
Olah, et al. Angew. Chem. Int. Ed. Eng. 1973, 12, 173.
>
H
H
H
Leveling the Field

The 3-center, 2-electron bond changes how all carbocations are precieved
Ethyl cation: hyperconjugation or hypervalence?
H
H
H
vs.
Me
vs.
H
H
- Rapid scrambling of 5 H's in ethyl cation indicative

of some delocalized intermediate
- Hydride shifts in such cations are illustrative of the low
energy barriers between cabenium and carbonium ions
H
Me
H
H
H
H
- Carbenium ions are prone to rearrangement
Me
Me
- Carbonium intermediate is calculated as favorable for

all but most stabilized carbocations
Leveling the Field

H
H
H
vs.
Me
vs.
H
H

H
Me
H
H
H
H
Me
Me

Leveling the Field

H
H
H
vs.
Me
vs.
H
H

H
Me
H
H
H
H
Me
Me

Leveling the Field

H
H
H
vs.

H
Me
H
H
H
H
H
H
vs.
H
H
Me

Me
Me
Wagner-Meerwein shifts and isomerization

H
- 1 13C NMR Shift at -139 C

H
- Rearrangements occur ~ 3.1 x 107 Hz
A Whole New Ballgame...

Delocalized intermediates also participate in assisting leaving group departure
Prins-Pinacol reaction intermediate resembles a momentarily delocalized cation:
Nuc
OH
O
O
O
LA
OH
LA
Nuc
Many of the carbocationic rearrangements basic to organic chemistry can be associated with
nonclassical carbocationic intermediates.
Outline
1. Introduction
Carbocationic Cascades- Biosynthesis

- isolated from streptomyces
- precursor to pentalenolactone
antibiotics
OPP
farnesyl diphosphate
pentalenene
1,2 shift
H
H
H
1,2 shift
H
H
H
H
H
H
H
Tantillo J. Am. Chem. Soc. 2006, 128, 6172.
- H+
H
H
Carbocationic Cascades- Biosynthesis

OPP
farnesyl diphosphate
H
H
humulene
H
6- protoilludene
H
asteriscadiene
H
H
Tantillo J. Am. Chem. Soc. 2006, 128, 6172.
W.S. Johnson's Approach to Steroid Skeletons

O
O
TFA, nitroethane
-78C, 15 min
HO
80% yield
Johnson, W. S.; et. al.

Journ. Am. Chem. Soc.
1973, 95, 4417.
O
TFA, TFE
-100 C
66% yield
OH
OH
SnCl4, DCM
30 min, -100 C
H
H
59% yield
HO

1976, 98, 1038.
HO

1973, 95, 7501.
W.S. Johnson's Approach to Steroid Skeletons

O
O
TFA, nitroethane
-78C, 15 min
80% yield

1973, 95, 4417.
O
TFA, TFE
-100 C
66% yield
SnCl4, DCM
30 min, -100 C
H
H
59% yield
HO

1976, 98, 1038.
HO

1973, 95, 7501.
Carbocationic Cascades- Corey and Oleananes

O
MeAlCl3
MeO
AlMeCl2
-78 C
O
O
PhCOCl
DMAP
H
BzO
HO
H
BzO
(+) -amyrin
R= CH3
(+) erthrodiol
R= CH2OH
(+) oleanolic acid R= COOH
H
HO
Corey, E.J J. Am. Chem. Soc. 1993, 115, 8873-8874
Some other unique rearrangements

H
MeAlCl2
-95 C
O
H
Cl2MeAl
Ph
HO
50% yield
Ph
Ph
Me
Ph
Cl2MeAl
Me
O
H
Ph
Cl2MeAl
Ph
Ph
O
H
Cl2MeAl
Me
Me
O
H
HO
Corey, E. J.; Roberts, B.E. Tetrahedron Lett. 1997, 38, 8921.
Me
Me
Me
Me
Me
Ph
Me
Cl2MeAl
Ph
Cl2MeAl
Cl2MeAl
Ph

N
RO
HO
RO
O
DAST
O
R
O
R
Et
N
SF3
Et
Lartey, et. al. J. Org. Chem. 1996, 61, 5153.

N
RO
HO
RO
O
DAST
O
R
O
R
Et
F
N S
Et
Et
F
N S
Et
Et
O
N S
O
Lartey, et. al. J. Org. Chem. 1996, 61, 5153.
Et
Cationic Cascade to Longifolene
TFA, Et2O HO
0 C, 3 min
HO
K2CO3 workup
76% yield
longifolene
H+
H+
HO
HO
K2CO3
Johnson, W. S., et. al. J. Am. Chem. Soc. 1975, 97, 4777.
Tantillo, D. J., et al. J. Org. Chem. 2005, 70, 5139.
Larry Overman and the Prins-Pinacol
N
H
O
H
H
OH
Me
H
()-magellanine
TIPSO
SnCl4
H
O
H
H
-78 C
H
57% yield
O
Overman, L. E. J. Am. Chem. Soc. 1993, 115, 2992.
OH
H
N
H
O
H
H
OH
Me
H
()-magellanine
TIPSO
SnCl4
H
H
-78 C
OH
57% yield
O
TIPSO
H
O
Me
Me
O
TIPSO
Me
Me
TIPSO
Overman, L. E. J. Am. Chem. Soc. 1993, 115, 2992.
AcO
O
H
O
OAc
H
shahamin K
O
OTMS
DMTSF
SPh
SPh
Me Me
SPh
-45 C to 0 C
80% yield
Overman, L.E. J. Am. Chem. Soc. 2001, 123, 4851
AcO
O
H
O
OAc
H
shahamin K
O
OTMS
SPh
SPh
Me Me
-45 C to 0 C
80% yield
OTMS
Me
Me
SPh
SPh
OTMS
Me
DMTSF
Me
SPh
Overman, L.E. J. Am. Chem. Soc. 2001, 123, 4851
Summary and Parting Thoughts

- The nonclassical carbocation controversy opened the realm of physical organic
chemistry, established the idea of delocalized, electron-poor bonding in
intermediates and transition states for organic reactions, and encouraged an
intense debate that has led to the affirmation of many instrumental and
experimental techniques used today
- The 3-center, 2-electron bond is prevalent in carbocation chemistry, often as a
stable intermediate or transition state, and sometimes as a stable molecule itself
- Carbocation chemistry and its variants have found an effective place in
synthesis, but there exists a large gap in controlled carbocationic methodology
that has only recently been explored.
Thanks to JT for the Carbocation book and Meyer for helpful advice

Non Classical Carbocations

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Non Classical Carbocations

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Nonclassical Carbocations

From Controversy to Convention

A Stoltz Group Literature Meeting

- 6 valence e- planar structure

The Nonclassical Problem: Early Curiosities

Meerwin, H. Chem. Ber. 1922, 55B, 2500.

The Nonclassical Problem: An Indecent Proposal

Winstein, Trifan. J. Am. Chem. Soc., 1949, 71, 2953.

The Nonclassical Problem: An Indecent Proposal

Enantiomerically pure starting material...

Winstein, Trifan. J. Am. Chem. Soc., 1949, 71, 2953.

1:1 Mixture of enantiomers

The Nonclassical Problem: An Indecent Proposal

Winstein, Trifan. J. Am. Chem. Soc., 1949, 71, 2953.

1:1 Mixture of enantiomers

The Nonclassical Problem: An Indecent Proposal

The Nonclassical Problem: An Indecent Proposal

The Nonclassical Problem: An Indecent Proposal

The Response of the Traditionalists- H. C. Brown

Solvolysis proceeds through unassisted ionization:

Brown, H.C. J. Am. Chem. Soc. 1964, 86, 1248-1250.

A Bonding Experience- Brown's Challenge

"The norbornyl cation does not possess sufficient electrons

A Bonding Experience- Brown's Challenge

"The norbornyl cation does not possess sufficient electrons

A Bonding Experience- Brown's Challenge

"The norbornyl cation does not possess sufficient electrons

Enter George Olah

shift was 300 ppm

J. Am Chem. Soc. 1964, 86, 1360

- Superacids designed to prevent proton elimination to quench carbocations

- pKa's are measured anhydrously by Hammet acidiy function Ho

Proving the Existence of the Carbonium Ion

NMR Studies of Olah, Saunders and Schleyer

Broad singlet corresponds

Resolves 3 singlets, 4:1:6

Proving the Existence of the Carbonium Ion

NMR Studies of Olah, Saunders and Schleyer

Broad singlet corresponds

Proving the Existence of the Carbonium Ion

spectra at low temps

Olah, G. A. J. Am. Chem. Soc. 1982, 104, 7105.

Proving the Existence of the Carbonium Ion

spectra at low temps

Olah, G. A. J. Am. Chem. Soc. 1982, 104, 7105.

Proving the Existence of the Carbonium Ion

Olah, G. A.; Mateescu, L. A. J. Am. Chem. Soc. 1970, 92, 7231.

Proving the Existence of the Carbonium Ion

Olah, G. A.; Mateescu, L. A. J. Am. Chem. Soc. 1970, 92, 7231.

Closing the Debate

Solid-state 13C NMR studies at 5 K

Isolated crystals allowed x-ray determination of

Laube, T. Angew. Chem. Int. Ed. Engl. 1987, 26, 560

For an excellent review of the nonclassical ion

Yannoni, C. S.; Myhre, P. C. J. Am. Chem. Soc. 1982, 104, 7381-7383

Other Important Nonclassical Carbocations

- Parent for all nonclassical carbocations.

- initially suggested trigonal bipyramidal structure

Olah, G. A.; Klopman, G. J. Am. Chem. Soc. 1969, 91, 3261

Other Important Nonclassical Carbocations

Studies by Roberts in 1951:

Other Important Nonclassical Carbocations

Studies by Roberts in 1951: