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ARTICLE

Methane activation by metal-free Lewis acid centers only — A

computational design and mechanism study
Published on 24 March 2016. Downloaded by Gazi Universitesi on 08/04/2016 18:00:12.

Received 00th January 20xx,

Accepted 00th January 20xx Gongli Ma, and Zhen Hua Li*
DOI: 10.1039/x0xx00000x

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.

through hydrogen-atom transfer to generate methyl radicals.

Introduction
Hydrocarbons are ubiquitous in the organic world, yet a lot of
them cannot be conveniently converted to synthetically
valuable compounds.1,2 In particular, the selective
functionalization of methane is an extremely tough challenge
for synthetic chemists because methane possesses high C-H
bond strength, negligible electron affinity, large ionization
energy, and low polarizability.3 Exploiting them efficiently as
more useful chemical raw materials or more available
functional substances is one of the hottest research fields for
chemistry researchers. To achieve the goal, the pivotal step is
to cleave the unreactive C-H bonds. Numerous experimental
and computational studies have been reported that breaking
C-H bonds can be acquired by using transition metal (TM)
complexes as catalysts.4,5 However, the drawback in terms of
economic and environmental factors becomes a strong spur to
develop metal-free strategies. With respect to metal-free
methane activation, some radical ionic oxides6 such as
[P4O10]•+,7 [SO2]•+,8 [CO]•+,9 [SiO]•+ 10 can activate methane
Efforts, meanwhile, have also been directed to develop closed-
shell molecules in consideration of the extreme instability of
free radicals or radical cations. Since the discovery of the
11
frustrated Lewis pairs (FLPs) by Stephan and co-workers, a
growing number of metal-free molecules/systems have been
found capable of activating small molecules such as
12 13 14 15
hydrogen, carbon dioxide, nitrous oxide, alkynes, sulfur
16 17
dioxide and ammonia under ambient conditions. The C-H
activation of heteroarenes by FLPs is considered to be “a leap
18,19
ahead for activating C-H bonds”. It is known by means of
the computational and experimental studies that the unusual
reactivity of FLPs is due to the intermolecular or
intramolecular combination of unquenched Lewis acid and
20
base centers. However, there is no experiment report on
methane activation by FLPs as far as we know. One
explanation is that the CH3 moiety of methane in the middle of
the Lewis acid and base hampers the efficient interaction of
the vacant orbital of the Lewis acid with the C-H σ bonding
orbital of methane, which reduces the Lewis acidity of FLP in
21
cleaving the C-H bond of methane. A few FLPs, which are
energetically favorable to activate methane, could be
computationally designed with an activation mechanism of the
side-on attack of methane through a cyclic transition state
(TS), and can be attributed to the synergistic interaction
between the acidity of the Lewis acid and the basicity of the
22
Lewis base.

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Silylboranes, the B-Si compounds, have incredible diversities
in synthetic chemistry because of the abundant substitutions
23-26
on the boron atom and the silicon atom. Their synthetic
methods have been reviewed in detail in ref. 23 and 24. The
electronegativity difference and the distinct reactivity of the
boryl and silyl groups are likely to make silylboranes easier to
react with target molecules by chemoselective activation of
27-30
the B-Si bond. B-Si bond activation not only has been

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Figure 1. Structures of the designed silylboranes for methane activation.

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31,32
applied to the functionalization of C-C multiple bonds but
also is a reliable method for the functionalization of C-Het (Het
33
stands for atoms other than C.) double bonds such as C=O,
34
C=N, etc. Meanwhile, the functionalization of strained-ring
35 36
compounds and cycloadditions of multiple-bond systems
by silylboranes are also the promising research fields in organic
syntheses.
To the best of our knowledge, there has barely been any
attempt to utilize silylboranes to activate the C-H bond of
methane. Inspired by the previous experimental and
computational studies about C-H activation by metal and
37-39
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metal-free catalysts, herein we report a systematic study
on the mechanism and reactivity of silylboranes in activating
the C-H bond of methane. Based on the energetic results of
methane activation by a large amount of silylboranes with
different substituents, a comprehensive data analysis40,41 has
been performed to unveil the relationship between the
reactivity of the silylboranes and the electronic properties of
the boron and silicon centers. The analysis leads to a much
deeper understanding of methane activation by metal-free
Lewis acid. Side reactions and solvent effect have also been
taken into account for a more effective guidance of the
experimental feasibility.
Computational details
The quantum chemical calculations in this work were all
42
performed with the Gaussian 09 software package. All
geometry optimizations of the reactants, products, transition
states, and intermediates were carried out at the M06-2X/6-
43
31+G(d, p) level. The M06-2X functional, developed based on
the Kohn–Sham density functional theory (DFT) by Zhao and
Truhlar, has proven to be very reliable for applications
involving main-group thermochemistry and kinetics. For the
molecules made up of main group elements, the M06-2X
relative energies were found to be reliable in alignment with
44
those at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ level.
In the present study, all the DFT calculations were performed
with a pruned (99,590) grid.
Harmonic frequency calculations were carried out not only
to provide zero-point energy (ZPE) and thermodynamic
corrections but also to guarantee that all minima have no
imaginary frequencies and all TSs have only one imaginary
frequency. Intrinsic reaction coordinate (IRC) calculations were
carried out to confirm the proper reaction channel between
45,46
the TS and its relevant minima. To obtain atomic charges
and Wiberg bond orders to analyze bonding characteristics,
47,48
the natural bond orbital (NBO) analyses at the M06-2X/6-
31+G(d, p) level were carried out. It is known that the entropic
contribution is ineluctably overestimated in the ideal gas
phase model. Consequently, we took solvation effect into
49,50
account for the system of interest. The SMD solvation
 ) of methane
51
model was used to compute solvation effect. In the following
study, all the calculations were first performed using the ideal
gas phase model and then followed by calculations with
solvation model.
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ARTICLE
By changing the substituents on the boryl and silyl groups,
we have designed a hierarchy of silylboranes, and they are
presented in Fig. 1. The first fourteen of them are treated as a
representative set that will be discussed in more details in the
text. The geometries and Cartesian coordinates of all the
Physical Chemistry Chemical Physics Accepted Manuscript
silylboranes, and the TSs and minima involved in the activation
of methane are available in ESI†. In the present study, the free-
≠
energy barriers (∆G ) at 298.15 K and standard state (1 atm in
gas phase or 1 mol/L in solution except for methane that is
always in gas phase.) are used to characterize the reactivity of
the silylboranes.
Results and discussion
Mechanism of methane activation by silylboranes
Learning from theoretical computations and matrix-isolation
studies on the existence of a weakly bound complex between
52
borane and dihydrogen (H3B…H2), the proposed activation
mechanism of dihydrogen is the side-on interaction of
dihydrogen with the Lewis acidic boron center first, then
forming a central (closed) three-center bond connecting the
53,54
two weakly bound hydrogen atoms with the boron atom.
The TS of the activation is shown in Fig. 2(a). The orbital
interaction of the H-H σ bonding orbital (  ) with the
unoccupied 2p orbital of B (2  ) plays an important role in the
formation of the H3B…H2 complex. In the present study, a
≠
relatively low ∆G of 11.9 kcal/mol was obtained, which is in
line with previous experimental observations and
computational results obtained with more sophisticated
method. By analogy to the reaction mechanism of dihydrogen
and borane, we optimized the homologous TS for the
activation of methane by borane (Fig. 2(b)) but obtained a
≠
much higher barrier (∆G = 28.5 kcal/mol). Based on our
cooperation experiences with experimentalists and simple
estimations based on the classical transition-state theory
Figure 2. Transition state structures of BH3 + H2 (a) and BH3 +
CH4 (b).
(TST), the reaction could be realized in mild conditions.
The preliminary calculations based on the above two model
reactions show that Lewis acid alone can activate small
molecules such as dihydrogen and methane. Further NBO
analyses of the TSs show that the interaction between  of
H2 or the σ bonding orbital of the C-H bond (
with 2  plays a key role in the activation of H2 and methane.
Considering that in the activation of methane by borane, the
breaking of the C-H and B-H bonds is compensated by the
formation of the B-C and H-H bonds, we were wondering
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whether the activation of methane would become easier if the
breaking B-H bond is replaced by a weaker bond and the Lewis
acidity of the boron center is also tuned by substituting H of
borane by other functional groups. In addition, although
borane has remarkable activity in activating methane, it is
as 610.8 kcal/mol. In fact, the interaction is so strong that a
three-center-two-electron bond (3CBond) can be viewed as
formed among C, H, and B. The NBO analysis with this 3CBond
gives an occupancy of 1.99 for this bond and the TS is
described by this Lewis structure better. In addition, the C-H σ

Physical Chemistry Chemical Physics Accepted Manuscript

∗
difficult to handle and is easily subjected to dimerization, anti-bonding orbital ( 
 ) of methane also has a strong
which makes the activation of methane actually much more interaction with the B-Si σ bonding orbital (
) with an E(2)
difficult in experiments. Inspired by the successful application
of silylboranes in synthetic chemistry, we designed a hierarchy
 to 0.33. As a
of silylboranes to activate methane.
Published on 24 March 2016. Downloaded by Gazi Universitesi on 08/04/2016 18:00:12.
value of 117.8 kcal/mol. This decreases the occupancy of 
∗
to just 1.68 while increases the occupancy of 
result of the donor-acceptor interactions between the two
pairs of orbitals, the NBO charge of the B atom decreases from

0.07e in M7 to -0.63e by 0.70e in the TS, and the net electron

transfer, which is 0.24e, is from methane to M7. From the
analyses we can see that the C-H bond of methane is
significantly activated due to the synergetic interactions
∗
between 
 and 2  , and between 
 and  . In addition,
the former interaction is much stronger than the later one, as
can be seen from the E(2) values and the net electron transfer.
As a result, the C-H bond is activated more than the B-Si bond.
These electronic structure analysis results are in accordance
Figure 3. (a) Transition state for methane activation by M7 and with the geometric data of the TS as discussed above.
(b) the HOMO and LUMO of M7. Bond lengths are given in Å.
According to previous computational studies, methane
activation by intramolecular B/N-based FLPs involves two
We start with the simplest silylborane, H2BSiH3 (M7 in Fig.
≠ critical orbitals.53 The HOMO and LUMO orbitals of the acid
1). The TS of the activation is shown in Fig. 3(a). The ∆G of the
and base are dominated by 2  and the lone pair orbital of N
reaction is 23.8 kcal/mol, which is lower by 4.7 kcal/mol than
(LPN), respectively. The activation of the C-H bond of methane
that of methane activation by borane. This gives us confidence
≠ stems from the synergistic interactions of two donor-acceptor
that the weaker B-Si bond in silylboranes does reduce the ∆G
pairs where 
 donates electrons to 2  and LPN donates
for methane activation. In addition, the reaction is exothermic ∗
electrons to 
 . However, in silylboranes there is no lone pair
and the Gibbs free energy of the reaction is -5.9 kcal/mol.
orbital as that of N in FLP. As shown in Fig. 3(b), the HOMO of
Therefore, methane activation by silylboranes is
M7 is dominated by  while the LUMO is dominated by 2  .
thermodynamically and kinetically practicable.
Therefore, to effectively activate the C-H bond of methane by
Similar to methane activation by borane, methane has a 
silylboranes one can either lower the energy of 2  ( ) or
side-on interaction with M7 in the TS. The C-H bond of
raise the energy of  ( ) or both. This can be realized by
methane is stretched noticeably from 1.09 Å in the free
changing the substituents on the B and Si centers. One might
methane to 1.40 Å in the TS. On the other hand, the B-Si bond 
expect that lowering  would increase the electrophilicity
is just elongated slightly by 0.05 Å to 2.07 Å. Both the C and H
and thus the acidity of the boron center according to the Lewis
atoms of methane are close to the B atom of M7 with an B-C
acid-base theory. This is similar to the use of FLP to activate
distance of 1.81 Å and an B-H distance of 1.25 Å. This is also
small molecules where the acidity of the boron center is tuned
similar to that of methane activation by borane. In both cases,
by the substituent groups on B.
the TSs are early TS where the C-H bond is significantly
activated and meanwhile short bonds between the boron
center and C and H atoms are formed. On the other hand, the
B-H bond in borane and the B-Si bond in M7 are just elongated
slightly. The geometric data indicate that in the TS, the C-H
bond is activated more than the B-Si bond.
More details of the activation process can be obtained from
NBO analyses on the electronic structure of the TS. The
analyses indicate that 
 of methane has a significant overlap
with 2  of M7 with 
 being the donor while 2  being the
acceptor. As a result of the interaction, the occupancy of 
 is
just 1.43, much lower than the expected value of 2.0 for a
single bond. On the other hand, the occupancy of 2  is 0.58,
which deviates significantly from the ideal value of 0.0 for an
unoccupied orbital. The analysis of the second order Figure 4. Variation of the Wiberg bond orders of the B-Si, B-C,
perturbation theory on the interaction between the two B-H, Si-H, and C-H bonds along the IRC. The vertical straight
orbitals indicate that the interaction has an E(2) value as high line represents the position of the TS.

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To gain further mechanistic insight into this activation
process, we carried out bond-order analyses for every
structure along the IRC reaction pathway. In Fig. 4, the Wiberg
bond orders of the bonds involved in the activation are plotted
with respect to reaction coordinate. As illustrated in the figure,
other hand, is due to the formation of the dative bond
between the Lewis acidic B center and the Lewis basic N center
of the cyan group. Other silylboranes might suffer different
problems. For example, although M30 and M35 have
extraordinary reactivity toward methane, they are not stable

Physical Chemistry Chemical Physics Accepted Manuscript

the evolution of bond orders of the breaking C-H and B-Si
bonds shows similar trend and the two curves are parallel and
non-overlapping. The bond orders of both bonds decrease
along the reaction coordinate, but the bond order of B-Si (WBSi)
is always higher than that of C-H (WCH). At the TS, WBSi is still
higher than 0.7 while WCH is already lower than 0.3. This
Published on 24 March 2016. Downloaded by Gazi Universitesi on 08/04/2016 18:00:12.
since M30 would form an O-B bond while F on the CF3 group in
M35 may migrate to B with a very low energy barrier and thus
M35 would transform into a more stable structure. Therefore,
in this section we will design a hierarchy of silylboranes for the
following purposes: 1) To elucidate the factors that affect the
reactivity of the silylboranes toward methane; 2) To find out

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

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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

Physical Chemistry Chemical Physics Accepted Manuscript

M46 12.1 21.6 -5.3 -8.9 -0.05 2.16 0.93 -327.8 0.01 -27.9
H on B in M7 by F while M3 by Cl. Both F and Cl are electron
M47 9.1 18.6 -4.0 -7.7 0.17 1.43 1.05 -283.0 0.42 4.6
M48 14.8 25.1 -2.6 -9.5 0.41 1.45 0.91 -282.2 0.16 10.6
withdrawing groups. NBO charge analysis results indicate that
M49 18.4 28.7 -8.6 -9.2 0.42 1.45 0.91 -292.7 0.16 11.3 the charge on B (qB) of M2 does become more positive
M50 18.1 28.4 -3.2 -5.7 0.44 1.47 0.91 -298.2 0.15 12.0 compared with M7 (0.56 vs 0.02, see Table 1). However, qB of
M51 12.7 23.2 -2.3 -4.9 0.21 1.54 0.86 -319.6 0.16 -9.7 M3 remains almost the same as that of M7. On the other

M52 26.6 36.2 -2.8 -5.5 0.33 2.22 0.89 -314.6 0.13 1.3 hand,  does lower greatly for M3 but it raises for M2.
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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,
replacing H on Si in M5 by ethyl (Et) or ethoxyl (OMe) group
has the same effect where the ∆G≠s for M13 and M14 are the
methane are plotted vs various electronic properties of the
silylboranes to characterize the boron and silicon centers.
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

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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

Physical Chemistry Chemical Physics Accepted Manuscript

  !
a weak positive correlation with  with an r of 0.39 and  
 , all other terms are cross terms. To find out how
≠
has fairly strong positive correlations with qB and  , with r prominent the influence of each property on ∆G we did two
being 0.64 and 0.71, respectively. Clearly, statistical methods analyses. The first one we chose three silylboranes with low,
≠ ≠
should be applied to find the relationship between ∆G and middle, and high ∆G 's, and varied each of the six properties
these electronic properties. by ±s where s is the standard deviation of the corresponding
property. The silylboranes we selected are M35, M44, and
≠
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Relationship between free-energy barrier and electronic
properties of the silylborane
Polynomial models have been proved to be simple but
appropriate for fitting and forecasting free-energy barriers of
chemical reactions.57 We employed the least-square fitting
method to fit the first 50 ∆G≠s (training set) in Table 1 with
respect to the six properties to obtain a good model for these
M36, with ∆G s of 15.7 kcal/mol, 37.4 kcal/mol, and 74.0
kcal/mol, respectively. The changing of ∆G≠ (∆∆G≠ = ∆G≠(s) -
∆G≠(-s)) predicted by Mod2 are presented in Table 2. The entry
MA (mean absolute value of ∆∆G≠ for each property) of Table
2 indicates that ∆G≠ is affected more by the properties on B.
Inspecting the MA values in Table 2 reveals that among the
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  )  )   ) 
  )!  
 
 )" # #   )$ #   )%  

  
 )& #    )'  

  
 )( # 
  )
 

The fitted parameters are -118.6, 143.2, 272.6, -0.005547,

37.43, 0.8733, -47.90, -0.2586, -506,4, -1.524, and 0.8889 for
a0 to a10, respectively, and -97.71, 119.4, 333.7, -0.007002, -
0.1022, 0.9200, 0.002767, 0.0007769, -236.5, 0.1529, and
1.092 for b0 to b10, respectively.
Excluding the constant, three terms of the two models are
  
the same and they are  , #  , and
  . The rest 7
terms in Mod2 are just the corresponding terms in Mod1 ≠
 !  
multiplied by a variable, for example 
 is 
 in Mod1 Figure 7. Scatter plots of the derivatives of ∆G vs. single
 

multiplied by
 
,   
is  in Mod1 multiplied by properties.
 , and etc. Since Mod2 is much better than Mod1, we will The second analysis we performed is calculating the
focus our discussion on Mod2. ≠
derivatives of ∆G with respect to the properties of the

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silylboranes. The tabulated results can be found in ESI†. Here
we present a graphical view of these results in Fig. 7. Similar
conclusions can be deduced from the results where all

preliminary calculations with TST, we tentatively set a
≠
somewhat arbitrary threshold of 33.0 kcal/mol for ∆G .
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

Physical Chemistry Chemical Physics Accepted Manuscript

≠
that the increase of the corresponding property will raise ∆G similar size. Appling the threshold 28 out of 57 candidates are
and vice-versa for negative derivatives. The results therefore left.
≠
indicate that in order to lower ∆G , i.e. to raise the reactivity of The second consideration is the dimerization of the
the silylboranes, we may change the substituents on B and Si silylboranes. This rules out those compounds with BH bonds
 
, or to lower
 , or to lower  . The increase in
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to raise 
and with =O, –O–, –NH2, and –CN substituent groups with
qB by using electron-withdrawing substituents on B, counter-
intuitively, does not help in most cases: Most *∆  /*# are
positive, which implies that increase in qB would raise ∆G≠. To

lower  , we should avoid the use of substituents in which
the atoms directly bonding to B have lone pairs such as
halogens, nitrogen, phosphorus, oxygen, and sulphur. These
substituents will donate electrons to 2pB. Substituents with π
bonds that can delocalize electrons to 2pB should better be
avoided. In practice, however, aromatic substituents are often
used and this can be compensated by adding electron-
withdrawing groups to the aromatic rings, e.g. C6F5. To lower

 , electron-withdrawing groups such as C6F5 on B can be
used. However, we should keep in mind that they may raise


 as well. Last, our model not only fits the data in the
training set well (see Fig. 8(a)), but also has fairly good ability
for prediction (see Fig.8(b)).
Consideration of experimental feasibility
For theoretical predictions to be realized by experiments, not
(a) (b)
≠ MeSi(CH2F)3 and MeSi(CH2Cl)3 to mimic M28 and M57,
Figure 8. Comparison of the ∆G s predicted by Mod2 and the
≠
calculated ∆G s in the training set (a) and testing set (b).
only the reactivity of the silylboranes should be considered,
but also other factors such as side reactions should be
considered. Due to the limitation of computational studies that
are in some sense idealized, we cannot consider all
possibilities. Nevertheless, we will try our best to design
several candidates with promising reactivity toward methane
that might be realized in not so harsh experimental conditions.
The first consideration is the reactivity of the silylboranes.
According to the classical TST, ∆G≠ is directly related to the
reaction rate of a reaction, thus we would expect the lower
the ∆G≠ is, the higher reactivity of the silylborane is. Based on
our cooperation experiences with experimentalists and
8 | Phys. Chem. Chem. Phys., 2016, 00, 1-3
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strong Lewis basicity. These compounds can easily form dimer
by either forming B-H-B 3Cbonds or dative bonds between
Lewis acid and base. This further rules out 10 from the 28
candidates.
The third consideration is the self-destruction21 of the
silylboranes. The C-H bond of methane is one of the most
difficult C-H bond to activate. The candidates thus should
better not contain easily accessed and activated C-H bonds.
This rules out those silylboranes with methyl, methylene,
methylidyne or unsubstituted phenyl groups. This rules out 11
from the remaining 18 candidates and only seven are left. The
seven candidates are M5, M12, M18, M23, M28, M35, and
M57. M5, M18, and M35 all contain at least one SiH3 group
and its Si-H bond can be easily activated by the silylboranes.
Using SiH4 as the model for the SiH3 group, our results show
that the activation of SiH4 by M5 to form (C6F5)2BH + Si2H6 has
an ∆G≠ of just 17.6 kcal/mol, much lower than that of
activating methane by M5, which is 32.3 kcal/mol. The
remaining four candidates are then M12, M23, M28, and M57,
and all of them have the same boryl group that is (C6F5)2B.
M12 and M23 contain a silyl group with three fluorine
substituted phenyl groups (see Fig. 1). The use of fluorine to
replace H on the phenyl group is to protect the neighboring C-
H bonds of the fluorine atoms. Due to electrostatic repulsion
the phenyl C-H bonds in M12 and M23 are well protected.
Using fluorobenzene to mimic the phenyl groups in M12 and
M23, we found the ∆G≠ for the activation of the ortho C-H
bonds in fluorobenzene by M12 is 39.6 kcal/mol, higher than
the 32.4 kcal/mol for methane activation. On the other hand,
the silyl group of M28 is Si(CH2F)3 while that of M57 is
Si(CH2Cl)3. The presence of F and Cl protects the C-H bonds on
the silyl groups from being activated by M28 or M57. Using
respectively, we found that the ∆G≠s for activating the C-H
bonds of the CH2F and CH2Cl group by M28 and M57 increase
by 6.9 kcal/mol and 14.5 kcal/mol, respectively.
Last, we consider solvent. Obviously, solvents such as
benzene and cyclohexane that contain methyl, methylene, or
unsubstituted phenyl groups cannot be used since they might
be activated by the silylboranes. In previous experiments
cyclohexane was used as a solvent for TM-mediated methane
activation.58 However, we found that cyclohexane cannot be
used as solvent since the ∆G≠ for the activation of cyclohexane
C-H bond by M12 is higher than that of methane by just 1.2
kcal/mol. In addition, the chosen solvent should be better to
≠
lower ∆G . We found that for the four candidates their TSs all
have larger dipole moments than the corresponding
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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

Physical Chemistry Chemical Physics Accepted Manuscript

≠
∆G s for methane activation by M12, M23, M28, and M57 are Financial support from National Natural Science Foundation of
32.8 kcal/mol, 34.7 kcal/mol, 28.9 kcal/mol, and 30.4 kcal/mol, China (No. 21273042 and 21573044) is gratefully
≠
respectively. The ∆G for M23 in solution is higher than the 33 acknowledged. We thank the super computer center of Fudan
kcal/mol threshold and we decided to remove it from our final University for computer time.
≠
list. Although the three ∆G s are still a little bit high, it should
≠
be noted that the ∆G s can be further lowered by increasing
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