346

ARTICLE
Exploration of the ␣-effect by substitution on hydroxylamine
anions. I. Effects of alkyl- and fluoroalkylation
D. Afzal and K.R. Fountain
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Abstract: Many explanations for the ␣-effect have been suggested. Most are simple models conjecturing various sources
affecting the nucleophilic behavior. This paper provides a comprehensive study of electronic effects using the single ␣-atom lone
electron pair of substituted hydroxyl amine anions. This substituent scheme shows that the interaction of this lone pair with the
negatively charged oxygen atom is an important indicator of reactivity.

Key words: natural bond order (NBO), overall barriers, single electron transfer, resonance.

Résumé : Beaucoup d’explications de l’effet alpha ont été proposées, la plupart du temps sous la forme de modèles simples
supposant que diverses sources pouvaient influencer le comportement nucléophile. Le présent article décrit une étude exhaus-
tive des effets électroniques réalisée à partir du doublet non liant de l’atome situé en position ␣ d’anions d’hydroxylamine
substitués. La présente substitution montre que l’interaction de ce doublet non liant avec l’atome d’oxygène chargé négative-
ment un signe important de réactivité. [Traduit par la Rédaction]

Mots-clés : orbitale de liaison naturelle (OLN), ensemble des barrières d’activation, transfert électronique unique, résonnance.

Introduction and background tum mechanical issues supporting this simple presentation of
For personal use only.

A recent report on the subject of the ␣-effect has shown the
existence of a gas-phase ␣-effect experimentally.1 The ␣-effect has
been modeled previously in several theoretical modes. An early
one is the Hoz model (Fig. 1).2 This model is based on valence bond
(VB) theory methods, particularly those initiated by Shaik and
Pross.3 The definitions of ␣-nucleophiles and normal nucleophiles
are shown in Scheme 1.
The effect in Fig. 1 is that the single electron being transferred
from the ␣-nucleophile invests less energy in making the transi-
tion than the normal nucleophile from the nucleophile to the
highest unoccupied orbital of the substrate.
The Shaik and Pross model of SN2 reactivity is presented in the
form of state correlation diagrams as shown in Fig. 2A.3 The major
features of these diagrams in Fig. 2A are the VB wave functions for
the reactants, labeled as ␺a wave function, and for the product, ␺b,
as shown with appropriate notations of the VBs at the bottom of
each figure. Higher level wave functions ␺c and␺d show a cationic
form and a single electron transfer from both the nucleophile and
the leaving group to the carbon atom being transferred. This last
VB structure, ␺d, is what is meant by SET (single-electron transfer)
in the remainder of this paper.
The transition states (TS) are shown at the midpoint of the
reaction coordinate where the reactant ␺a and the product ␺b
wave functions are expected to cross each other. Because their
energies are equal, the avoided crossing (or noncrossing) rule
holds. These wave functions are said to “repel each other” with
the result that the actual TS occurs at the top of the hill at the
highest actual point allowed along the reaction coordinate. This
point is designated by the dashed curve of the lower of the two
noncrossing wave functions. The difference in the energy from
the crossing point to the TS is labeled B and indicates quantum
mechanical resonance energy.3 Detailed discussion of the quan-
noncrossing are available.4,5
The result of noncrossing of the two wave functions ␺a and ␺b is
that stabilization at the TS is increased or decreased by interac-
tions of ␺c and ␺d with the crossing reactant and product VB wave
functions. The greater the cationic contribution, the less stabili-
zation via B. The larger the SET contribution, the larger is the
B energy. These interactions affect the stabilization and the larger
the value of B. Both cationic and SET wave functions ␺c and ␺d
thus influence the energy content of the TS.
This scheme gives a simple way to study the ␣-effect by using a
system with only a single electron lone pair on the adjacent atom.
This scheme avoids possible ancillary interactions by the adjacent
atoms, such as oxygen atoms with additional lone pairs, as in
HOO−.
The present paper examines substituted hydroxylamine anion
reactivity with methyl fluoride in computations of the TSs. The
use of RNHO− or RR=NO− as substituted ␣-nucleophiles offers the
advantage of two different sites to substitute on the nitrogen
atom, allowing assessment of the overall barrier energy starting
from the most reactive reported ␣-nucleophile, NH2O−. Acquiring
the slope of such a systematic linear free energy plot allows as-
sessment of the reactivity to electron pair manipulation by the
substitution in a systematic way and allows including mixed sub-
stituents. The resonance scheme for a ␺d wave function has the
form of an aminoxyl radical in the nucleophile, without produc-
ing a fully neutral species, since the positive charge on nitrogen
atom and the negative charge on the oxygen atom produces some
charge separation contribution.6,7,8 Scheme 2 shows resonance
forms for such a species.
Alkylation of the nitrogen atom should give increasing and
decreasing inductive effects, or other effects, included in such
aminoxyl-like structural variations in Scheme 2. Examples of dif-
ferences in spin density are available from both experimental and

Received 3 June 2013. Accepted 24 January 2014.

D. Afzal and K.R. Fountain. Chemistry Department, Truman University, Kirksville, MO 63501, USA.
Corresponding author: D. Afzal (e-mail: sc18@truman.edu).

Can. J. Chem. 92: 346–353 (2014) dx.doi.org/10.1139/cjc-2013-0246 Published at www.nrcresearchpress.com/cjc on 10 February 2014.
 Afzal and Fountain
Fig. 1. Hoz model for the ␣-effect.
Scheme 1. The ␣-nucleophile has the nucleophilic electron pair
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 05/26/14
next to an atom with a lone electron pair. The normal nucleophile
has no neighboring lone electron pair.
Fig. 2. State correlation diagrams.
For personal use only.
Scheme 2.
theoretical studies. Reports of theoretical work show that reso-
nance is a factor in both the nitrogen atom spin density and the
oxygen atom spin density of aminioxyls, while other studies, at
computation levels, without diffuse functions, and employing
largely mp2/6-31* or 6-31** basis sets, showed differences in ni-
trogen pyramid inversion barrier with (CHF3)2NO and Me2NOami-
noxyls, with the fluorinated species having the higher inversion
barrier.7
One particularly useful paper shows that the aminoxyl stability
for several classes of substituted aminoxyl is greater than the
isolated R• + R=−N = O species, giving RR=N−O• radicals.8 These
computations also were at a basis set level that mostly omitted
diffuse functions. The importance of these concepts is focused on
what a substituted aminoxyl fragment would look like with two
VB wave functions that would perturb ␺d.9 Scheme 3 shows how
the two VB wave functions in an aminoxyl format appear as the
perturbing system for ␺d in Fig. 2B.
347
Scheme 3. Lewis structure representations of the two VB wave
functions contributing to ␺d in SN2 reactions.
Fig. 3. Positive and negative overall barriers.
It might be expected that some particular substitution by alkyl
groups on the nitrogen atom would, at least partially, stabilize the
B resonance contributor more than the A form, in which case the
perturbed ␺d would be opposite that shown in Fig. 2B, with the per-
turbation curve pointed downwards on the right side of the TS
maximum. This event would lessen stabilization compared with
the alternate left side perturbation and would only help stabilize
the reverse reaction. If the stability for the A VB contributor
should be greater than for the B VB contributor, the ␺d would look
like the form in Fig. 2B. This left side of Fig. 2B contains the
contribution to the overall barrier energy in the ␣-effect.
The purpose of this paper is to investigate the reactivity indica-
tors of nitrogen-substituted hydroxyl amine anions RNHO− and
RR’NO− in gas-phase Brönsted-type regression studies. These stud-
ies plot theoretical gas-phase acidities (GPA) (equivalent to basic-
ity), versus the overall barriers, defined as the difference between
the enthalpy of the two initial reactants and the enthalpy of the TS
for their reaction. A simple representation of an overall barrier is
presented in Fig. 3. In this figure, an overall barrier can be either
a negative (exothermic) or a positive value (endothermic). Both
are shown in Fig. 3, since the TS can be approached from either
side of the diagram.
These Brönsted-type plots will be presented in figures that also
include the already known results for simple ␣-nucleophiles, for
example, ClO−, BrO−, FO−, HOO−, etc. These comparisons will be
shown as several regression lines in a single figure that includes
lines for the RHNO− and RR=NO− ␣-nucleophiles in color and the
known and published normal nucleophiles in black and white.
Likewise, the fluorinated alkyl species are presented in color. The
regressions for the RHNO− and RR=NO− species and the (RFx)NHO
and (RFx)(R=Fy)NO species are in separate Brönsted-type plots of
the figure to give adequate clarity. These presentations allow as-
sessment of the differences that substitution with fluorine atoms
makes on the behavior of ␣-nucleophiles on the reactivity. This
kind of study fills the role of a series of critical computational
experiments. If no unusual behavior increasing or decreasing the
␣-effect occurs when the population on the nitrogen lone electron
pair (NLP) is seen to change, or the interaction between the NLP
and the oxygen atom charge, then the entire theory that the NLP
affects are important and that these items are involved in the
reactivity of the anions necessarily must be discarded. The elec-
tronic effects of these substituted systems are investigated in
three ways.
First, the issue of how the substitutions affect the determina-
tions of ␣-effects related to the known ␣-nucleophiles with
Brönsted-type plots is studied. These plots would investigate the
Published by NRC Research Press
 348
effects of substitutions on the >NO− anion system on the sizes of
the ␣-effects compared with those obtained with the known, pub-
lished systems of ␣-nucleophiles relative to normal nucleophiles.
Second, the role of negative charge on the oxygen atom inter-
action related to the lone pair population on the nitrogen atom
will be investigated. This will sort out the relationships between
the natural resonance theory percentages of the VB-like localized
wave functions that describe that single electronic transfer reso-
nance.
Third, the role of SET in affecting the overall barriers is ex-
plored in regression-like plots. This gives the assessment of the
role of SET in various substitution patterns for the substituted
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NO− system. Inclusion of substitution of vinyl groups allows as-
sessment of ␲ orbital mediation effects, such as polarization of
the carbon atom attached to the nitrogen atom via polarized ␲
orbitals. These are expected to be very different from the other
interactions between the NLP and oxygen atom and are studied by
relating the NLP population with the charges on the oxygen atoms
in the TSs.
Methods
The tool of increasing electron demand, and its corollary the
tool of electron supply, makes possible the investigation of the
roles of an electron demand or supply involving the NLP similar to
the effects on alkoxide oxygen lone pairs.10,11 The TS overall bar-
riers were determined using Gaussian 03W or Gaussian 03 (via
WebMO) using CBS-QB3(Startmp2)⶿mp2∕6-31 + G(d)⶿hf⶿6-31+G(d) in
a linked job format (the order of applied operations goes from
right to left in these expressions with the hf applied first).12 This
For personal use only.
procedure has the effect of obtaining a G2(+) geometry, with the
post-Hartree−Fock energy via an adequate method. The geome-
tries are thus equivalent to those previously reported by other
workers elsewhere.13,14,15
It is not sufficient to merely show that reactivity increases or
decreases, but such an increase/decrease must be compared with
factors that change the reactivity of the normal nucleophiles used
to determine the ␣-effect. The tool available is the natural bond
order (NBO) population determination.16,17,18 The initial NBO-type
results in this paper deal only with the natural resonance theory
(NRT) and populations and charges. Among the lists of these res-
onance structures, there appears one or two that show SET char-
acter, with the long-bond spin pairing required by VB theory.5 It is
thus possible to attempt to assess the relationship between the
electron population on the nitrogen and oxygen atoms with the
degree of SET transfer to the methyl group (Me). The SET role of
the NLPs in the TSs (which must be regarded as singlet pathways)
affects each single electron from the oxygen atom in the SET. This
electron coupled with one of opposite spin is involved in ␺d, from
the fluorine atom, giving a long bond formation. In some cases,
the percentages of SET contributions for the different ␣ and ␤
spins were not the same. An example is for Me2NO− where the
NBO resonance structures for ␣ and ␤ electrons give unequal sums
of weights for VB structures. This observation gives an indication
that the NLP VB weights lone pairs sum to different values, and
none sum to a 100% of lone pair on nitrogen. In these cases, the
sum of the two spin designations (percentage of total structures)
are reported as SET%, containing the contributions from both ␣
and ␤ spins. Consider Scheme 2 where the substituted NO− group
is either monoalkylated or dialkylated substituted. This system
would allow either a SET or a pair transfer resulting in different
behavior in analysis of electronic effects. If ␺(d) B were to be a
major contributor, a larger change to the effect of the two-electron
transfer would ensue.
Scheme 3 shows two VB-type resonance structures descriptive
of the aminoxyl-type contribution to the nucleophile structure
corresponding to the VB contributor ␺d in Fig. 2B. An SN2 reaction
of hydroxyl amine anion ␺d in the state correlation diagrams
Can. J. Chem. Vol. 92, 2014
would have these two contributors, A and B, in Scheme 3. These
two wave functions would both contribute stability attributed to
three-electron bonds within the nucleophiles and employed in
explaining Fig. 1.2
The VB weighting coefficients of these contributors will be im-
portant for two reasons. First, the amount of SET from both the
nucleophile and the leaving group affects the amount of contri-
bution of ␺c, the cationic contributor (triple ion), at the avoided
crossing point. This in turn affects the quantum mechanical res-
onance energy B which would be greater if this cationic contribu-
tion is less. This conclusion is arrived at by considering that ␺a and
␺b are the major contributors in forming the TS, which are mod-
ified by the other two upper energy contributors. The B value
turns out to be dependent on ␺c for the cationic contribution. The
lower the contribution of this VB component, the greater is the B
stabilization. In a simple SN2 reaction, as in Fig. 2A, the VB weights
of these upper contributors. The amount of ␺c will be lessened by
an increase in ␺d contribution. The formula for B uses eq. 1.5 The
definition of Qa indicates that if ␭c is small, the B value is large and
the more stable the TS will be. If the SET contribution from ␺d is
increased, the contribution of the triple ion is less, since normal-
ization requires that the net sum of the component squares of
their weights must be 1 (or 100%). The amount of SET contribution
thus affects overall barriers significantly. This lowering of the TS
energy at the top of the dotted line in the state correlation dia-
grams would mean greater reactivity for the nucleophile. In
addition, stabilization of 1B by increasing the stabilizing of the
electron pairs on oxygen with the nitrogen-radical-like form would
perturb the contribution of ␺d, as in Fig. 2B:
B ⫽ QMRE ⫽ 0.5 × D0(1 ⫺ Q a)
(1)
Q a ⫽ ␭trpion
2
/(␭trpion
2
⫹ 1)
where ␭ is the weight of ␺c and D0 is the dissociation energy for the
C−F bond in the substrate.
Calculation of quantum mechanical resonance energy
The noncrossing rule applies for these two resonance VB func-
tions ␺c and ␺d and would thus lower the overall energy of the
pathway from the reactant side, thus giving a larger B value and a
lower TS energy.19 Exploring this concept requires experimenting
with a system that allows the NLP to be manipulated in the TS to
give both A and B contributors as in Scheme 2 and to measure
their VB weighting fractions with the NRT method. Most elemen-
tary organic chemistry textbooks make the point that both carbon
radicals and carbon cations are stabilized by substitution of hy-
drogen atoms by alkyl groups. The similar point (will a nitrogen
atom radical also be so stabilized by additional substitution of
fluorine on carbon for hydrogen as in fluoroalkyl substituents
atoms?) is part of this study. A VB study using GENNBO NBO
theory and NRT to ascertain the relative populations in the nu-
cleophile at the TS (A and B) is quite useful for this purpose and is
included within a strong computational system, Gaussian 03W.12,16
Substitution by alkyl groups for the N−H bonds of H2NOH affords
this kind of manipulation.
Results
Comparing the overall barrier values of substituted R1R2NO−
anions with the established barriers of more simple ␣-nucleophiles
and normal nucleophiles should indicate electronic effects on the
nitrogen atom and of the substituted NO system. These computa-
tions were carried out and the results are shown in Table 1 and
plotted in Fig. 4. The black points in Fig. 4 are the already published
data as Brönsted-type plots from our previous paper for the simple
␣-nucleophiles and normal nucleophiles.20 The black line plots rep-
resent the established computational data for gas-phase ␣-effects
and serve as points of comparison with the substituted NO− system.
Published by NRC Research Press
 Afzal and Fountain 349

Table 1. GPA, overall barriers, and UHF SET for RHNO− and RR=NO− nucleophiles.
Overall barrier Overall barrier
RHNO− GPA (kJ/mol) UHF SET RR=NO− GPA (kJ/mol) UHF SET
1 H3SiNHO 1481.3 53.2 2.49 1 (H3Si)2NO 1457.4 49 6.06
2 2-PropenNHO 1532.8 13.9 5.41 2 (CH2CH)2NO 1515.1 37.3 10.78
3 CH2CHNHO 1536.7 11.4 11.03 3 AllylMeNO 1555.5 −4.5 5.34
4 HOCH2CH2NHO 1569.7 −6.1 6.95 4 EtMeNO 1566.2 −4.7 13.69
5 t-BuNHO 1576.8 −12.6 4.74 5 (CH2CH2)NO 1562 −3.5 19.3
6 n-PropNHO 1577.5 −6.8 5.4 6 Et2NO 1566.7 −6.7 6.91
7 (CHCHCH)NHO 1577.6 −17.9 5.19 7 (CHCH)NO 1568.2 −3.4 8.1
8 AllylNHO 1577.7 7.9 4.34 8 Me2NO 1613.2 −32.5 16.02
9 MeOCH2CH2NHO 1579.5 −13.2 6.62
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10 i-ProNHO 1580.7 −11.1 3.28

11 CyclopropanNHO 1584.6 −9.8 18.8
12 EtNHO 1589.3 −14.6 9.83
13 MeNHO 1592 −13.3 8.28

Fig. 4. Brönsted-type plots for RNHO− and RR=NO nucleophile GPA ence in monosubstituted fluoroakyl and disubstituted fluoroalkyl
versus overall barrier. anions, since they plot on different lines. The red line shows that
most of the RH(Fx)NO points plot closely but slightly above the
black line of simple ␣-nucleophiles.
The outliers are shown by a color ot box. For example, 5ot shows
this singly fluoroalkylated group and is close to the green line
(RFx)(R=Fx)NO plot, indicating a sharp change when the number of
fluorine atoms is small and separated away from the NO system.
The green line for the (RFx)(R=Fy)NO− anions shows significant scat-
ter. Some points are close to the simple ␣- nucleophiles black line.
These results indicate stronger influence of the NO− anion system
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occurs to cause some of the (RFx)(R=Fy)NO− anion systems, with

These combinations of several Brönsted-type plots are useful for
comparing the alkylated (RR=)NO− anions’ reactivity to determine
the effect of the number of alkyl groups on the nitrogen atom.
Some points may plot lower on the overall barrier axis than the
best standard ␣-nucleophiles but have slopes that trend toward
the normal nucleophile line. This, indeed, occurs in Fig. 4,
indicating that the RNHO− and RR=NO− nucleophiles have similar
characteristics because they both contain examples of ␣-nucleophile
activity that depends on how the substituent affects the ␣-effect.
These plots show that straight lines with reasonable regression
results are usually obtained. Some lines have some points as out-
liers (ot) that also contain information on effects on the NO− sys-
tem but are not included in the regressions. The effects of alkyl
groups (some of which are fluorinated) were important in the
previous paper on the normal nucleophiles (with C−O as the site of
reaction), causing some of these normal nucleophiles to become
more reactive than the simple ␣-nucleophiles.20 It is important to
also explore this effect with both sets of mono- and difluoroal-
kylated NO− ␣-nucleophiles. These results are presented in Table 2
and Fig. 5. The potential role of the NLP in the TSs of the variously
substituted nucleophiles was examined by comparing the NLP
populations with the charge on the oxygen atom are summarized
in Tables 3 and 4 and Figs. 6 and 7. Outliers also occur in some of
these plots, which are indicated with color ot symbols.
The relationship between the NLP and the charge on the oxygen
atom in the TS was determined with NBO theory.16,17,18 The plots
of the oxygen atom charges versus the NLP populations are dis-
played in Figs. 6 and 7 and recorded in Tables 3 and 4. The RFNHO
and (RFx)(R=Fy)NO anions plot in Fig. 5 shows considerable differ-
fluorine atoms on carbon atoms directly attached to the NO sec-
tion, to become better ␣-nucleophiles. Point b on this line indi-
cates that inclusion in a three-membered ring decreases the
reactivity but leaves a substantial ␣-effect. Point 2 has even more
fluorine atoms close to the NO− anion system.
Figure 6 shows plotting of NLP versus the oxygen atom charge
in the TSs and shows that the alkyl-substituted systems plot fairly
regularly in both RHNO− and RR=NO− systems, with the exception
of the (H3Si)2NO− anion, which shows a relative decline of charge
on oxygen with declining NLP population. The series of points
indicate disubstitution clusters near the high-NLP high oxygen
atom charge corner of the plot, which indicates relatively small,
but significant changes around the alkyl- and dialkylated NO−
anions. Comparing these two similar clustering arrangements of
points in Figs. 4 and 6 shows that these points might be mutually
reflecting each other. The outlier in Fig. 6 is (H3Si)2NO− but it has
a higher overall barrier than C2F5NHO−. The position of NH2O− in
Fig. 6 indicates that the same NLP number generates large charge
on oxygen, where it is not conjugated with 2 pi systems. Figure 6
indicates a low overall barrier for NH2O−; thus, it is definite that a
change in overall barrier is connected with dispersion of the NLP
population.
The fluorine-containing substituents in Fig. 7 show quite differ-
ent behavior. The black line shows the mono- and dialkylated
substituents from Fig. 6 plotted together as a comparison index in
Fig. 7, indicating an adequate regression of the alkyl and dialkyl
cases. The (RFx)NHO− and (RFx)(R=Fy)NO− plots show quite different
regression behavior than those on the black line for the alkylated
nucleophiles line. Both of these cases show much more scatter along
the respective regression lines compared with the alkyl and dial-
kyl species and slopes similar to each other but very different
from the alkyl group species. The green line for (RFx)(R=Fy)NO− has
only modest regression numbers, indicating that some anions
resemble the alkylated anions closely, while other points depart
widely from the alkylated plot. The RFxHNO plot shows substan-
tial scatter with a very poor regression coefficient.
The C2F5NHO− point in Fig. 7 (ot1) is very unusual; it has an NLP
population that is one of the highest, but the oxygen charge is one

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 350 Can. J. Chem. Vol. 92, 2014

Table 2. GPA and overall barriers for RFxHNO− and (RFx)R=Fy)NO− nucleophiles and UHF SET%.
Overall barrier Overall barrier
RFxNHO− GPA (kJ/mol) (kJ/mol) UHF% RFxR=FyNO− GPA (kJ/mol) (kJ/mol) UHF%
1 CH2FCF2NHO 1488 12.9 2.55 1 (CF3)2NO 1435.4 34.4 0
2 CF3NHO 1509 7.7 7.56 2 TetFCycNO 1438.5 41.2 10.74
3 CHF2NHO 1523.5 2.07 5.17 3 (CHF2)NO 1453.2 28.4 5.17
4 CH2FCH2NHO 1532 10 4.04 4 (CH2F)(HCF2)NO 1488.1 26.4 2.55
5 CF3CH2NHO 1537.1 0.63 1.78 5 (CH2F)2NO 1506.2 20.7 3.67
6 CH2FNHO 1545.8 −2.3 3.49 6 (FCHFCHtr)NO 1503.4 14.8 5.71
7 AllylFNHO 1538 3.5 9.36
8 C2F5NHO 1489 12.3 12.3
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Fig. 5. Brönsted-type plots for (RFx)HNHO− and (RFx)(R=Fy)NO− fects are reflected in the clustering of alkyl- and dialkylated NO
reacting with methyl fluoride. anions in Fig. 6 in the section of high-NLP population, high charge
on oxygen. These closely related points indicate a large NLP pop-
ulation and a large charge on oxygen consistent with a large ␺dA-
type anion contribution, shown in Scheme 3, with a fractional
anion instead of a radical on oxygen (i.e., −0.78 rather than ap-
proximately −0.83).
The increasing ␣-effects (differences between the points of the
black normal nucleophile line and the black ␣-nucleophile line)
usually observed with the established ␣-nucleophiles as the GPA
becomes smaller are reduced by alkyl- or dialkyl-substituted NO−
systems as these lines slant toward the black normal nucleophile
lines. These trends indicate that alkylation affects the size of the
␣-effects in a manner dependent on the position of the point in
Fig. 4 on the GPA line, with smaller ␣-effects for smaller GPA
values. The slopes (susceptibilities) define Brönsted ␤ values to
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evaluate reactivity plots.19 Two kinds of ␤ values are now known,

of the smaller ones. Comparing Fig. 4 with Fig. 6 and Fig. 4 with
Fig. 7 (where the slopes in Fig. 5 indicate similar values for the
singly and difluroalkylated substituents) shows singly fluoroal-
kylated >NO− anions giving overall barriers close to the estab-
lished ␣-nucleophiles. However, the (RFxR=Fy)NO− anions produce
␣-effects smaller than the established ones, which have larger
overall barriers. These observations indicate major differences in
Fig. 7 indicating great involvement of the relationships between
the NLP population and the charge on oxygen in the TS. The
(H3Si)NO− group in Fig. 6 plots as though it was equivalent to a
point in the RFxNHO− group in Fig. 7.
Discussion
These observations indicate that the substituted NO anion sys-
tem responds in different ways to the groups attached to it. In the
far right section of Fig. 4, the point for the Me2NO− anion gives the
lowest overall barrier of all the ␣-nucleophiles, including the sim-
ple ␣-anions. Progression in the x-axis direction toward lesser GPA
in Fig. 4 for the alkylated and dialkylated NO system indicates that
some RNHO− ␣-anions behave very much like the simple ␣-anions
in the larger GPS (right side) of the GPA. At lower GPA values,
these anions plot as normal nucleophiles, even plotting above the
black normal nucleophile line. In Fig. 5, both the RFxNHO− and
RFxR=FyNO− points never plot below the standard ␣-nucleophiles
line but give points lying along and slightly above the black line of
the standard ␣-nucleophiles or on a line nearly parallel to that
line. The clustering of both alkylated and dialkylated NO anions in
the region of GPA from 1550 to approximately 1600 in Fig. 4 shows
that the effects of these alkyl groups are all quite similar giving
nearly the same ␣-effects, with small differences. Electronic
features of these TSs might be expected to resemble each other
closely yet demonstrate the small differences in Fig. 4. These ef-
␤nuc and ␤lg, referring to one for the nucleophiles and one for the
leaving group. In the present paper, ␤nuc is used, since the leaving
group is always F−. The size of the ␤nuc is said to be 0.0 > 1.0. Larger
␤nuc values are reported for reactions in solution.21,22
Figure 4 shows that ␤nuc values for the simple ␣-nucleophiles
are small, approximately 0.3. The normal nucleophiles have a ␤nuc
value of 0.46. The substituted R1R2NO system has a ␤nuc of 0.4921
for disubstituted and 0.648 for monosubstituted. These numbers
indicate that the alkyl substitution on nitrogen introduces some
factor in the hydroxylamine anion that causes the ␤nuc value for
the RR=NO anions to resemble the ␤nuc value of the simple nucleo-
philes, whereas the singly alkylated set has ␤nuc values much
larger. Considerations of the size of ␤nuc values have been re-
ported in several venues.19–25
A particularly interesting instance involves measurement of
␤nuc values in formation of Meisenheimer-type ␴ adducts that are
formed in furazan derivatives.26 In these types of compounds,
large ␤nuc values, 1.0 and 1.3–1.4, outside of the formal limits
(0.0 < 1.0) were associated with an SET mechanism, i.e., fast initial
SET from the aniline-type nucleophile. An alternative model in-
volved a strong inductive effect in the negatively charged ni-
trofurazanyl structure, leaving a greater positive charge at the
developing aniline nitrogen atom. These authors stated that ob-
taining an abnormally large ␤nuc may indicate an electron trans-
fer (SET) in the nucleophilic attack, which would lend credence to
the proposal that SET is operative greatly in the present data.
In a situation such as shown in Fig. 4, obtaining a larger ␤nuc
value in the singly alkylated NHO anion might be consistent with
increased SET character in a VB presentation of an SN2-type reac-
tion scheme. Consider also Fig. 5, the Brönsted-type plot for
RFxHNO− and (RFx)(R=Fy)NO− systems, comparing these anions
with the simple ␣-nucleophiles and normal nucleophiles. The im-
portant feature of Fig. 5 is the comparative size of the ␤nuc for the
simple ␣-nucleophiles with the size of the ␤nuc value for the blue
line of the RFxHNO− group. Figure 5 indicates that the RFxNHO−
anions (+) behave similarly to simple known ␣-nucleophiles, with
a few serious outliers, and the trend of this line is to cross the line

Published by NRC Research Press

 Afzal and Fountain 351

Table 3. Comparing RHNO− and RR=NO− NLP population and oxygen charge at TS geometries.
RNHO− NLP Charge on O RR=NO− NLP Charge on O
1 CH2CHNHO 1.84293 −0.7451 1 (CH2CH)2NO 1.6695 −0.6786
2 H3SiHNO 1.92345 −0.7693 2 (H3Si)2NO 1.8958 −0.7231
3 EtNHO 1.96265 −0.7933 3 Me2NO 1.9281 −0.7781
4 CycCHCHCHNHO 1.93998 −0.787 4 EtMeNO 1.9311 −0.7933
5 MeNHO 1.95858 −0.79 5 Et2NO 1.9319 −0.7684
6 i-PropNHO 1.96103 −0.7835 6 (CH2CH2)NO 1.9899 −0.7878
7 MeOCH2CH2NHO 1.96221 −0.784
8 AllylNHO 1.96694 −0.7815
9 HOCH2CH2NHO 1.96364 −0.7833
10 t-BuNHO 1.96146 −0.7952
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 05/26/14

11 NH2O 1.9922 −0.8149

Table 4. Comparing RFxHNO− and RFxR=FyNO− NLP population and charge on oxygen at TS geometries.
RFxNHO− NLP Charge on O RFxR=FyNO− NLP Charge on O
1 C2F5NHO 1.91031 −0.6511 a TetraFCycNO 1.83019 −0.6421
2 CF3NHO 1.91554 −0.7228 b (CF3)2NO 1.87827 −0.6545
3 CHF2NHO 1.91723 −0.7426 c (CHF2)2NO 1.89368 −0.6952
4 CH2FNHO 1.92152 −0.7663 d (CH2F)2NO 1.92654 −0.8511
5 CH2FCH2NHO 1.95939 −0.7745 e (CH2F)MeNO 1.93458 −0.7537
6 CF3CH2NHO 1.96454 −0.8824
7 Allyl2FNHO 1.97353 −0.7651

Fig. 6. Comparing NLP population with charge on oxygen. normal ␣-nucleophile black line as the GPA decreases (GPA indi-
cates gas-phase basicity also). This line shows considerable scatter
similar to the fluroalkanols reported in Afzal and Fountain,20
For personal use only.

where these fluroalkanols began to show overall barriers similar

Fig. 7. Comparing RFxNHO− and (RFx)(R=Fy)NO− with RNHO and
RR=NO.
for the simple ␣-nucleophiles. This implies the possibility of ob-
taining RFxHNO anions that would be better nucleophiles than
the simple known ones.
The (RFx)(R=Fy)NO− nucleophiles plot (triangles) line is signifi-
cantly above those of the simple ␣-nucleophiles black line or the
RFxNHO− nucleophiles, and additionally, they slope toward the
to the overall barriers of the simple ␣-nucleophiles, leading to
deceptive conclusions about whether or not a gas-phase ␣-effect is
present in the comparative data for the available sets of points.20
The outstanding feature of Fig. 5 is the similarity of the
mono- and difluroalkyl NO systems. The ␤nuc values for the simple
␣-nucleophiles, the red regression line, and the green regression
line are similar but the green line is displaced upward toward the
normal nucleophiles. The ot5 looks like a disubstituted case but is
actually a monosubstituted species, with fluorine atoms farther
away from the nitrogen atom. This indicates a change in influence
on the nitrogen atom when a few fluorine atoms are moved away
from the nitrogen atom leaving a set of C−H bonds adjacent. Point
c shows a point from the disubstituted set plotting back on the red
mono-Fx-alkylated NO system when additional fluorine atoms are
placed on the remote atom. These facts and the analysis so far lead
to the important expectation that substitution on the nitrogen
atom can control the sizes of the overall barriers, relative to the
already established ones. These substitutions are able to alter the
␤nuc values in opposite directions, perhaps implying opposite
trending electronic effects or conformational effects.
The first possibility was examined by evaluating the way the
populations of the NLP affect the charge on the oxygen atom in
the TSs. Figure 6 shows an analysis of the role of charge on oxygen
for the known ␣-nucleophiles compared with the substituted NO−
nucleophiles (the data are from calculations within this paper). It
is clear from Fig. 8 that alkyl substitution causes a large difference
in the role of oxygen charge between this system and the simple
known ␣-nucleophiles.
Figure 6 shows the regression plot of the NBO charge on the
oxygen atom with the NLP population in alkyl-substituted sys-
tems (RHNO and RR=NO). The mono- and disubstituted plot shows
a fairly regular pattern in both mono- and disubstituted cases with
several outliers, an outcome that supports a distinct effect of the
NLP on delivery of charge on the oxygen atoms for displacement
of the F− anion. The lowest charge value for the oxygen atom is in
the (CH2CH)2NO− substitution, which also corresponds to the low-
est NLP population.

Published by NRC Research Press

 352
Fig. 8. Comparing the charge on oxygen versus overall barriers of
known ␣-nucleophiles with RHNO− and RR=NO−.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 05/26/14
The vinyl substitution is the lowest NLP population for the
monosubstituted set. These substituted systems appear in Fig. 4 as
outliers designated by ot8 and otb with the divinyl being on the
normal nucleophile line and the vinyl being on the red line for the
␣-nucleophiles. These findings indicate conclusively that effects
on the NLP affect the overall barrier energies.
The fluoroalkyl-substituted hydroxylamine NLP population ver-
For personal use only.
sus charges on oxygen for the TSs is shown in Fig. 7. The deviations
from the alkyl and dialkyl anion systems are shown with the black
line. The scattering is much more extensive, as shown by the
regression coefficient values, but the slopes are similar in the
fluoroalkylated set. The outliers are significant because the (H3Si)2NO−
point resembles a difluoroalkyl item.
The most highly fluorinated point, (C2F5NHO−), shows the NLP
population as high as the highest alkyl cases but has the lowest
charge on oxygen, lower than (CF3)2 and nearly as low as (CF2CF2)NO−.
Both of these latter cases can be considered as completely flu-
orinated alkyl-disubstituted cases. Previously, the result of large
amounts of fluorine substitution on alcohols was to cause large
lone pair repulsion away from the fluorinated section of the al-
kanol anion, making them better nucleophiles in displacing
halogen atoms from methyl groups, i.e., making these “normal
nucleophiles” appear as reactive as ␣-nucleophiles.20 This repul-
sive behavior is well attested to.27
Finally, the relationships between the SET numbers and the
overall barrier are displayed in Fig. 9 for monoalkyl and dial-
kylated NO− ␣-nucleophiles. The outstanding feature of Fig. 9 is
that the NO− system nucleophiles divide into five families, all of
which have different slopes, implying that different substitution
patterns on NO− systems will give different contributions of SET
in their SN2 TSs with methyl fluoride.
The single cyan line (solid inverted triangles) containing the
divinyl, 2-propenyl, and allyl groups possessing a positive slope
indicates that for these compounds, the increasing SET contribu-
tions also increase the overall barrier values, in contrast with all
of the members of the other families where decreasing overall
barrier values occur with increasing SET contributions.
The negative slopes of the other families indicate a direct rela-
tionship between SET increase and lowering of overall barriers.
This supports the thesis that differing VB weighting factors for
␺d A and ␺d B from Scheme 3 may be responsible for the responses
of the values of the overall barriers. These findings indicate, at
least, a reason for widely different notions of whether or not an
␣-effect occurs in a particular set of data.
Can. J. Chem. Vol. 92, 2014
Fig. 9. UHF SET versus overall barriers.
Summary
Brönsted-type plots showing comparisons of monoalkylated
and dialkylated NO− ␣-nucleophiles show greater ␤nuc values for
these types of nucleophiles than for the previously published
␣-nucleophiles. Some of these monoalkylated >NO− plot outside
(higher overall barrier) the line for the established normal nucleo-
philes and this must mean slower reactions than normal nucleo-
philes. This finding indicates the possibility of the existence of
negative ␣-effects (␣-nucleophile overall barrier higher than nor-
mal nucleophile; ␣-effect = normal overall barrier − ␣-nucleophile
overall barrier.
In monofluoroalkylated and difluoralkylated NO− nucleophiles
in Fig. 5, the regression lines behave oppositely from the simple
alkylated NO− system lines, having slopes very similar to the es-
tablished ␣-nucleophile line, or slightly less, causing potentially
larger ␣-effects in the lower GPA region of 1400–1425. The difluoral-
kylated NO− line closely parallels the established ␣-nucleophile
line but involves slightly higher overall barrier values. This
line contains some outliers that moved closer to the simple
␣-nucleophile line, indicating that the fluorination in these cases
produces greater nucleophile similar activity to the cases of fluo-
roalkoxides in Afzal and Fountain.20 The NLP population affects
the charge on oxygen in the TSs with only mild scatter with the
NO system but much greater scatter in the RFxHNO− family and
with even more scatter in the (RFx)(R=Fy)NO− group.
The relationships between SET VB character and the overall
barrier values dictate families of closely regression-related fami-
lies. Four families in Fig. 9 indicate negative slopes where increas-
ing SET decreases the overall barrier. One family displays a
positive slope and that indication supports the theory that reso-
nance in the sense of Schemes 3A and 3B can be manipulated to
give different VB weighting values to the two resonance forms to
produce widely differing results in the values of the overall barriers.
These outcomes make good sense if the resonance forms in
Scheme 3 are taken into consideration. The various effects of the
weights for the VB contributors discussed in this paper should be
expected to give such variety. Where the contributor weights are
small and similar for a series of substituted NO− anions, there
should be similarity in the behavior of those TS overall barrier
values.
Conclusions
These results together make a case that the scheme in Scheme 3
and the resonance structures A and B provide much insight into
the sometimes mysterious determinations of opinions of the ex-
istence of or nonexistence of the gas-phase ␣-effects. Each of the
experiments reported in the Summary section above are designed
to be a risky computational experiment, as described in the Intro-
duction and background section. If any one of them was found to
have no outcome, that would support the theory that the ␣-effect,
at least partly, is conditioned by electronic factors that affect op-
erations of the ␣-effect in the TS. If no involvements of the ␣-atom
lone pair are involved, these negative outcomes would result in
Published by NRC Research Press
 Afzal and Fountain
rejection of the entire theory that the ␣-lone pair is important and
that another source of the ␣-effect should be sought.
The differential substitution shows that different substitutions
on the nitrogen atom give different Brönsted-type plots. Simple
alkyl group substitutions give lines that plot increasingly toward
the simple normal nucleophiles, whereas the fluorinated alkyl group
substitutions give lines plotting toward the simple ␣-nucleophiles.
The NLPs of these alkylated and fluoroalkylated groups are related
to the charge on the oxygen atom in the TS. The relationship
between SET and the overall barriers discloses the existence of
families of relationships. For this reason, the theory that elec-
tronic effects are modified by action with the lone pair of the
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Depository Services Program on 05/26/14
␣-atom is a proper knowledge claim. “The ␣-effect depends on
electronic effects and participation of the lone pair.” To negate
this theory, a future experiment must be subject to the restric-
tions of a risky experiment, one that places the entire theory at
risk with a negative outcome. No such negative outcome is found
in any of these experiments.
The existence of families of relationships for SET values of sub-
stituted >NO− systems to overall barriers in Fig. 9 indicates that
many electronic factors may influence the magnitude of the
␣-effects. This issue was previously addressed by the present au-
thors in an ACS national meeting.28 The essential idea of critical,
or risky, experiments has been used previously to valid the
Woodward−Hoffman rules for conservation of orbital symmetry
by Berson.29,30 This method was an experimentally based valida-
tion. A more recent use employing the same principle of a risky
experiment refuted the theory that the ␣-effect was due to cou-
lombic attraction of the partially positively charged methyl group
For personal use only.
for a negatively charged ␣ atom.20 A positively charged ␣ atom in
a sulfur-containing ␣-nucleophile gave an ␣-effect larger than a
negatively charged ␣ atom, contrary to the electronic attraction
theory. Both examples establish that the use of critical (risky)
experiments applies in both experimental and theoretical venues.
Hoz and Buncel31 gives a very good example of early appraisal of
the ␣-effect. “The sources of the ␣-effect are remarkable in their
ambiguity.” The present paper, perhaps, offers the beginnings of
untangling these ambiguities.
Acknowledgements
The authors thank Truman State University for office space for
K.R.F. and Dr. Eric Patterson for a link to the university WebMo
network for the large jobs and discussions, and Dr. Mariah Nagan
for helpful comments. K.R.F. thanks D.A.F. for reading the manu-
script.
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