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www.rsc.org/ In the present computational study by using the density functional theory (DFT) method, we found that silylboranes, which
have metal-free Lewis acid centers only, can break the C-H bond of the exceedingly unreactive methane. The study shows
that, unlike the activation mechanism of small molecules by the frustrated Lewis pairs (FLPs), the Lewis acidic boron center
plays a key role on breaking the C-H bond of methane. Detailed analyses indicate that in the transition state the C-H bond
is substantially activated by the empty 2p orbital of boron (2pB) primarily due to the orbital interaction between the C-H σ
bonding orbital and 2pB. On the other hand, the orbital interaction between the C-H σ anti-bonding orbital and the B-Si σ
bonding orbital also contributes to the activation but plays a minor role. Statistical method was used to find the
relationship between the reactivity of 57 silylboranes and their electronic properties. The results indicate that the boron
center does have more prominent effect on the reactivity, especially the occupancy ( ) and energy ( ) of 2pB where
lowering and will raise the reactivity of the silylboranes. Based on the activation mechanism and taking kinetic and
thermodynamic possibility, as well as possible side reactions into consideration, three silylboranes suitable for methane
activation under mild experimental conditions were designed. the analogous line of thought can be used as a hint for
further experimental realizations, even under ambient condition. This strategy can also be expected to transplant to more
extensive C-H activation of hydrocarbons.
This journal is © The Royal Society of Chemistry 2016 Phys. Chem. Chem. Phys., 2016, 00, 1-3 | 1
Silylboranes, the B-Si compounds, have incredible diversities electronegativity difference and the distinct reactivity of the
in synthetic chemistry because of the abundant substitutions boryl and silyl groups are likely to make silylboranes easier to
23-26
on the boron atom and the silicon atom. Their synthetic react with target molecules by chemoselective activation of
27-30
methods have been reviewed in detail in ref. 23 and 24. The the B-Si bond. B-Si bond activation not only has been
2 | Phys. Chem. Chem. Phys., 2016, 00, 1-3 This journal is © The Royal Society of Chemistry 2016
This journal is © The Royal Society of Chemistry 2016 Phys. Chem. Chem. Phys., 2016, 00, 1-3 | 3
whether the activation of methane would become easier if the as 610.8 kcal/mol. In fact, the interaction is so strong that a
breaking B-H bond is replaced by a weaker bond and the Lewis three-center-two-electron bond (3CBond) can be viewed as
acidity of the boron center is also tuned by substituting H of formed among C, H, and B. The NBO analysis with this 3CBond
borane by other functional groups. In addition, although gives an occupancy of 1.99 for this bond and the TS is
borane has remarkable activity in activating methane, it is described by this Lewis structure better. In addition, the C-H σ
4 | Phys. Chem. Chem. Phys., 2016, 00, 1-3 This journal is © The Royal Society of Chemistry 2016
To gain further mechanistic insight into this activation other hand, is due to the formation of the dative bond
process, we carried out bond-order analyses for every between the Lewis acidic B center and the Lewis basic N center
structure along the IRC reaction pathway. In Fig. 4, the Wiberg of the cyan group. Other silylboranes might suffer different
bond orders of the bonds involved in the activation are plotted problems. For example, although M30 and M35 have
with respect to reaction coordinate. As illustrated in the figure, extraordinary reactivity toward methane, they are not stable
indicates that the cleavage of C-H is always ahead of B-Si. The some silylborane candidates with fairly high reactivity toward
evolution of the bond orders of the forming B-C and Si-H methane, but might be easy to synthesis and with as few side
bonds also has a parallel trend. They both increase along the reactions as possible.
reaction coordinate but the bond order of B-C (WBC) is always
higher than that of Si-H (WSiH). At the TS, WBC already reaches Table 1. Energetic data (all in kcal/mol) of the reaction:
about 0.7 while WSiH is just about 0.1. The results indicate that Reaction energy at 0 K (ΔE), reaction free energy at 298.15 K
the formation of B-C is much earlier than Si-H. (ΔG), energy barrier at 0 K (∆E≠), free-energy barrier at 298.15
We have to call attention to the evolution of the B-H bond K (∆G≠); Results of NBO analysis for the silyloranes: NBO
order (WBH). WBH firstly increases to its summit slightly after charges (in a.u.) of B (qB) and Si (qSi) atoms; Wiberg bond order
the TS and then decreases. At the TS, WBH reaches up to 0.5 of the B-Si bond (WBSi); energy of the bonding orbital of the B-
while at the summit it is about 0.6. These results clearly show Si bond (εBSi, in kcal/mol); occupancy ( ) and energy ( , in
that the C-H bond is firstly activated and broken by the boron kcal/mol) of the empty 2p orbital of B.
center with the formation of partially formed B-H and B-C TS Product Property of Silylborane
Silylborane
∆E≠ ∆G≠ ΔE ΔG qB qSi WBSi εBSi
bonds or a B-H-C 3Cbond and then the breaking of the B-Si
M1 58.5 67.2 2.1 -4.2 0.78 0.55 0.96 -308.7 0.34 18.7
bond and the formation of the Si-H bond. This further confirms
M2 46.1 55.6 -4.8 -7.1 1.00 0.45 0.97 -324.0 0.24 4.3
the finding that boron center plays a key role in the activation M3 33.1 43.3 -4.5 -8.0 0.06 0.60 0.95 -342.6 0.58 -80.3
of the C-H bond while the leaving Si group plays a minor role M4 25.2 36.6 -4.9 -5.1 0.49 0.56 0.98 -301.5 0.09 17.7
∗
since
has much weaker interaction with
and the B-Si M5 22.5 32.3 -1.4 -5.3 0.44 0.60 0.95 -325.3 0.19 -11.7
bond is only broken after the complete breaking of the C-H M6 14.4 24.5 -9.9 -10.2 0.26 0.61 0.92 -340.1 0.17 -22.8
M7 14.4 23.8 -7.5 -7.4 0.07 0.50 1.01 -317.0 0.02 -2.5
bond. This is different from the mechanism of the FLPs where
M8 28.2 40.7 -2.3 -4.9 0.37 1.72 0.87 -325.8 0.20 -2.6
both the acid and base centers involve in the activation M9 26.2 38.1 -3.0 -3.0 0.47 1.50 0.90 -324.5 0.18 -3.1
process deeply and synchronically in most cases. M10 22.8 35.1 -4.8 -4.9 0.44 1.47 0.89 -312.6 0.16 -1.1
M11 21.1 33.3 -4.4 -8.5 0.44 1.53 0.89 -327.1 0.18 -16.0
M12 20.3 32.4 -5.1 -7.7 0.44 1.53 0.89 -318.4 0.18 -10.0
Substituent effects
M13 19.1 30.2 -3.7 -7.9 0.44 1.53 0.89 -310.8 0.16 -2.3
M14 18.4 30.2 -2.9 -3.2 0.32 2.22 0.83 -327.5 0.18 -5.1
M15 27.4 38.9 -3.6 -3.5 0.45 1.51 0.90 -344.2 0.19 -30.8
M16 19.1 30.6 -2.5 -2.7 0.43 1.47 0.89 -310.9 0.17 -4.5
M17 25.7 35.6 -6.0 -4.9 0.45 1.24 0.91 -358.6 0.22 -34.9
M18 20.2 31.0 -18.4 -22.5 0.49 0.51 1.00 -337.8 0.21 -14.8
M19 26.4 38.3 -2.6 -8.6 0.46 1.50 0.90 -326.7 0.18 -11.3
M20 20.0 32.0 -2.8 -5.5 0.45 1.52 0.89 -311.6 0.17 -4.2
M21 18.4 29.1 -6.3 -5.9 0.42 1.45 0.89 -309.1 0.17 -4.0
M22 23.8 34.3 -5.8 -9.1 0.39 1.21 0.86 -352.0 0.20 -26.4
Figure 5. Optimized structures of the dimers of M7 (a) and M6 M23 21.6 32.4 1.5 0.2 0.44 1.53 0.89 -333.1 0.19 -21.1
(b). M24 18.8 29.9 -6.4 -9.5 0.43 0.91 0.92 -319.5 0.18 -9.2
M25 17.8 27.9 -5.6 -5.7 0.34 1.94 0.83 -317.1 0.18 -3.5
Although activating methane by the simplest silylborane is M26 26.9 37.0 -3.6 -8.3 0.46 0.57 0.97 -305.0 0.20 16.1
M27 21.7 32.4 -3.2 -6.4 0.45 0.88 0.93 -320.2 0.18 -6.2
thermodynamically and kinetically feasible, there is a gap
M28 19.5 29.6 -2.9 -7.5 0.42 1.32 0.91 -331.3 0.19 -12.8
between computational design and experimental realization. It M29 23.2 32.7 -5.8 -5.5 0.43 1.42 0.92 -290.5 0.18 22.9
is not just to find a silylborane with the highest reactivity M30 0.4 12.3 -5.6 -6.1 -0.15 0.60 0.93 -371.0 0.21 -74.8
toward methane. Many factors should be considered, such as M31 56.4 66.5 -0.6 -5.1 0.76 1.41 0.92 -295.3 0.40 112.5
side reactions, solvent effect, easiness of the synthesis of the M32 20.3 30.3 2.4 -3.8 0.48 0.56 0.97 -306.3 0.13 16.4
M33 28.6 39.1 -5.5 -8.5 0.41 0.57 0.97 -322.1 0.14 5.1
silylboranes, and etc. For example, a serious drawback of M6
M34 55.5 65.3 -5.5 -9.9 0.82 0.50 0.96 -305.5 0.34 17.3
and M7 is that they are easy to dimerize (as shown in Fig. 5). M35 4.8 15.7 -1.9 -7.9 0.37 0.56 0.96 -349.8 0.08 -32.7
The formation of the M7 dimer is due to its strong tendency to M36 64.0 74.0 -7.6 -10.1 0.51 0.58 0.97 -304.6 0.42 23.9
form the B-H-B 3Cbonds. To separate them an additional 25.7 M37 62.7 72.8 -4.3 -6.2 0.54 0.57 0.97 -306.1 0.44 20.5
M38 62.0 71.9 -7.1 -7.6 0.52 0.56 0.96 -293.8 0.48 112.9
kcal/mol is needed. The formation of the M6 dimer, on the
M39 56.4 66.3 -2.6 -2.9 0.58 0.55 0.96 -296.0 0.45 18.6
This journal is © The Royal Society of Chemistry 2016 Phys. Chem. Chem. Phys., 2016, 00, 1-3 | 5
M40 27.8 37.6 -5.4 -5.6 -0.45 0.63 0.96 -327.3 0.36 -36.3
The above analysis indicates that a single factor such as the
M41 25.9 36.5 -2.5 -6.4 0.53 0.56 0.98 -306.4 0.12 24.0
M42 29.7 40.0 -4.9 -4.9 -0.02 0.62 0.95 -348.2 0.75 -124.7
electronegativity of the substituent cannot be used as the
M43 27.3 38.0 -6.1 -6.9 -0.04 1.46 0.90 -332.5 0.74 -118.2 guideline to choose substituent groups. Substituents seem to
M44 26.4 37.4 2.9 -3.3 0.60 0.55 0.98 -308.7 0.11 28.6 have a profound influence on the reactivity of the silylboranes.
M45 11.2 21.8 -5.8 -6.9 0.22 1.46 0.86 -319.0 0.16 -11.6 Taking M2 and M3 as example, M2 was obtained by replacing
M53 26.6 37.9 1.5 0.2 0.44 1.19 0.89 -336.1 0.14 0.3 Inspecting the orbital interactions in M2 and M3 indicates that
M54 56.0 67.0 -4.5 -8.0 0.67 2.13 0.88 -297.4 0.34 22.9 although F and Cl do draw electrons from B through the F-B or
M55 12.2 21.3 -5.5 -8.5 0.05 1.41 0.96 -306.2 0.03 -0.9 Cl-B σ bonding orbital, they also donate electrons back to B
M56 44.6 54.3 -7.6 -10.1 0.97 1.30 0.93 -306.9 0.23 14.5 from their lone pairs to 2pB through the formation of π
M57 21.4 32.6 -2.0 -6.0 0.41 1.52 0.90 -334.7 0.20 -14.7 orbitals. The lone pair of Cl has higher energy than that of F
and thus has better overlap with 2pB. In addition, F has higher
Firstly, we focus on the substituent effect on the reactivity electronegativity than Cl. As a result, Cl donates back more
and activation mechanism of the silylboranes toward methane. electrons to B which increases the occupancy of 2pB ( ) from
In Table 1, the energy barrier at 0 K (∆E≠), the free-energy near zero in M7 to 0.58 in M3. In comparison, of M2 is just
barrier at 298.15 K (∆G≠), the energy change of the reaction at 0.24. These detailed analyses indicate that the Lewis acidity of
0 K (∆E), and the free-energy change of the reaction at 298.15 the boron center does not simply determined by the
K (∆G) are tabulated. Almost all ∆Es and ∆Gs are negative, electronegativity of its substituents. There are complicated
indicating that the reactions are thermodynamically feasible. interactions between the substituents and the boron center.
Here we will first examine the substituent effect of M1 to M14 Since a Lewis acid center is the acceptor of a pair of electrons,
in detail, seeking inspirations for the analysis on all the it is reasonable to deduce that not only and qB, but also
silylboranes latter. M1 to M7 were obtained by fixing the silyl may affect the Lewis acidity of the boron center. In
group to SiH3 while varying the substituents on B. On the other addition, the substituents on Si may also affect the electronic
hand, M8 to M14 were obtained by fixing the boryl group to structure of the boron center through the B-Si bond. For
B(C6F5)2 while varying the substituents on Si. In each class, the example, for M8-M14, not only WBSi and the charge on Si (qSi),
silylboranes are sorted according to the calculated ∆G≠ values but also qB, , and are affected by the substituents on Si.
in a descending order. Therefore, the factors that affect the reactivity of the
The results indicate that the substituent effect on ∆E and ∆G silylboranes are multiple and there may be reciprocal effect
is not prominent except for M8. It is possible that the higher among these factors also.
exothermicity of the reaction of M8 with methane is related to
the tert-butyl effect because of steric effects.56 On the other
hand, ΔE≠ and ∆G≠ have a much wider span than ∆E and ∆G,
implying a much more prominent effect of substituents on the
reactivity of the silylboranes. Obviously, the substituent effect
on B is more prominent than that on Si where from M1 to M7
ΔG≠ changes from 67.2 kcal/mol to 23.8 kcal/mol while from
M8 to M14 ΔG≠ changes just from 40.7 kcal/mol to 30.2
kcal/mol. This is in agreement with the above analysis on the
activation of methane by M7 that the boron center plays a
major role. It can also be seen that the substituent effect on
both B and Si is not so intuitive and straightforward. For
example, it is expected that replacing H on B by more
electronegative groups might lower and the Lewis acidity
of the boron center. However, the results show that replacing ≠
Figure 6. Scatter plots of the ∆G vs. single properties for all
H by other groups increases ΔG≠, no matter what their
silylboranes.
electronegativities are. Replacing H on Si with more
≠
electronegative groups might lower
and thus increase In Fig. 6 ∆G s of the reactions between all silylboranes with
∆G≠. However, the results are not as expected. For example, methane are plotted vs various electronic properties of the
replacing H on Si in M5 by ethyl (Et) or ethoxyl (OMe) group silylboranes to characterize the boron and silicon centers.
has the same effect where the ∆G≠s for M13 and M14 are the These properties are tabulated in Table 1 and they are qB, qSi,
same. WBSi,
, , and . No remarkable regularity can be
intuitively observed from these plots. More importantly, these
6 | Phys. Chem. Chem. Phys., 2016, 00, 1-3 This journal is © The Royal Society of Chemistry 2016
properties are not completely independent. The analysis of the First of all, all six properties we selected appear in the final
Pearson's correlation coefficients (r) among the 6 properties model. This validates our choice of the properties to
show that qSi has a fairly strong negative correlation with
characterize the reactivity of the silylboranes. Secondly, the
≠
with an r of -0.76, i.e. the B-Si bond can be weakened by influence of these properties on ∆G is not independent but is
increasing the positive charge on Si. On the other hand, qB has reciprocal. Except the second and third terms, i.e.
and
Relationship between free-energy barrier and electronic M36, with ∆G s of 15.7 kcal/mol, 37.4 kcal/mol, and 74.0
properties of the silylborane kcal/mol, respectively. The changing of ∆G≠ (∆∆G≠ = ∆G≠(s) -
Polynomial models have been proved to be simple but ∆G≠(-s)) predicted by Mod2 are presented in Table 2. The entry
appropriate for fitting and forecasting free-energy barriers of MA (mean absolute value of ∆∆G≠ for each property) of Table
chemical reactions.57 We employed the least-square fitting 2 indicates that ∆G≠ is affected more by the properties on B.
method to fit the first 50 ∆G≠s (training set) in Table 1 with Inspecting the MA values in Table 2 reveals that among the
respect to the six properties to obtain a good model for these three properties of B, the influences of
and are most
data. The last seven ∆G≠s were used as testing set to test the prominent. On the other hand, among the three properties of
predictive ability of the model. The seven silylboranes were Si, the influences of εBSi is most prominent. This is in
actually designed after we had successfully fitted the 50 data accordance with our NBO analyses on the TS of the activation
points. of methane by H2BSiH3 (M7). In addition, the influence of qB,
We started from the simplest model that ∆G≠ is the first qSi and WBSi on ∆G≠ is not consistent. For example, increase in
order polynomial function of the six properties (variables) and qB raises ∆G≠ for M35 but lowers ∆G≠ for M44. On the other
then gradually added second order and third order terms. The hand, the influence of εBSi, , and on ∆G≠ is consistent
best second order model (Mod1) we obtained by using the where increase in εBSi, or decrease in , or decrease in
≠
root-mean-square error (RMSE) as the criterion has an R2 of lowers the ∆G 's for all three silylboranes.
0.97, a mean unsigned error (MUE) of 2.0 kcal/mol, and a
maximum error of 6.7 kcal/mol. The third order model, which Table 2. The change of ∆G≠ (∆∆G≠ = ∆G≠(s) - ∆G≠(-s), in
was named Mod2, has an R2 of 0.98, an MUE of 1.6 kcal/mol, kcal/mol) by changing each one of the six properties by ±s and
and a maximum error of 6.0 kcal/mol. The detailed fitting the mean absolute value (MA) of ∆∆G≠.
procedure can be found in ESI† and the resulting two models qB qSi WBSi εBSi
are: M35 21.4 7.0 5.8 -7.9 20.0 11.6
M44 -4.8 18.2 6.9 -7.4 21.9 57.7
∆ Mod1
! M36 19.7 -9.1 -7.0 -27.1 67.8 37.6
" # #
$ # % #
MA 15.3 11.5 6.6 14.1 36.6 35.6
& #
'
(
!
∆ Mod2 ) )
) )!
)" # #
)$ # )%
)& #
)'
)( #
)
This journal is © The Royal Society of Chemistry 2016 Phys. Chem. Chem. Phys., 2016, 00, 1-3 | 7
silylboranes. The tabulated results can be found in ESI†. Here preliminary calculations with TST, we tentatively set a
≠
we present a graphical view of these results in Fig. 7. Similar somewhat arbitrary threshold of 33.0 kcal/mol for ∆G .
conclusions can be deduced from the results where all Moreover, there are just a few data points between 33
*∆ /*
values are negative while most *∆ /*
≠
and kcal/mol and 35 kcal/mol for ∆G and the threshold of 33
*∆ /* values are positive. Positive derivatives implies kcal/mol coincidently divides all 57 data points into two sets of
8 | Phys. Chem. Chem. Phys., 2016, 00, 1-3 This journal is © The Royal Society of Chemistry 2016
silylboranes. Therefore, solvents with high dielectric constant methane in 1,2-dichloroethane solution are 32.8 kcal/mol,
can be used. Finally, we chose 1,2-dichloroethane as solvent. 28.9 kcal/mol, and 30.4 kcal/mol, respectively.
≠
The ∆G for the activation of the C-H bond of 1,2-
dichloroethane by M12 is 44.2 kcal/mol, much higher than that
for methane activation. In the 1,2-dichloroethane solution, the Acknowledgements
the pressure of methane. Due to unexpected side reactions Notes and references
≠
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This journal is © The Royal Society of Chemistry 2016 Phys. Chem. Chem. Phys., 2016, 00, 1-3 | 9
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