Chemical Physics Letters 475 (2009) 188–192

Contents lists available at ScienceDirect

Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Theoretical study on the oxidative addition of methyl fluoride to Ru+

E. Bernabé, O. Méndez, F. Colmenares *
Departamento de Física y Química Teórica, Facultad de Química, Universidad Nacional Autónoma de México, México D.F. 04510, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: CASSCF–MRMP2 calculations have been carried out to analyze the interaction of the CH3F molecule with
Received 29 January 2009 Ru+. Potential energy curves for the electronic states emerging from the three low-lying states of the reac-
In final form 15 May 2009 tants were calculated for different approaching modes of the fragments. Whereas no favorable channels
Available online 24 May 2009
were detected for the insertion of the cation into the C–H bond of fluoromethane, stable products for the
oxidative addition of the C–F bond of this molecule to Ru+ were obtained for all the electronic channels
investigated. The asymptote corresponding to the fluorine abstraction products Ru–F+ + CH3 is above the
ground state energy of the reactants.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction In this contribution, some of the features of the pattern fol-

The activation of the C–F bond in fluorocarbon compounds by
transition metal containing systems is the subject of a growing
number of experimental and theoretical investigations, due mainly
to the interest in the potential applications that a controlled activa-
tion of this bond could have in catalytic processes [1–8].
In this line, the reactions of transition metal atoms or ions with
the methyl fluoride molecule constitute relatively simple systems
in which some of the features of the pattern followed by C–F bond
activation reactions can be analyzed both experimentally and the-
oretically [9–16]. The study of this kind of reactions also allows
analyzing the competition between the channels which lead to
the carbon–halogen bond activation and those involving the acti-
vation of the C–H bonds that are usually present in many fluorocar-
bon compounds.
Zhao et al. have investigated the gas phase reactions of methyl
fluoride with 46 different atomic transition metal and main-group
cations through mass spectrometry techniques [9]. In accord with
the results obtained by these authors, each of these reactions falls
into one of the following categories: addition of CH3F to the metal-
lic ion, fluorine atom transfer and H2 or HF elimination reactions.
The products obtained from the CH3F addition and the fluorine
abstraction channels are the preferred ones for most of the transi-
tion metal ions.
Theoretical results have also been reported for the reaction
of fluoromethane with some naked atoms or atomic cations
[10–16]. To our best knowledge, no theoretical studies have been
carried out on the reaction of methyl fluoride with the ruthenium
cation. For this reaction, the addition product Ru+CH3F has been
experimentally detected [9].
* Corresponding author.
E-mail address: colmen@unam.mx (F. Colmenares).
lowed by the reaction Ru+ + CH3F are discussed in terms of the po-
tential energy curves belonging to the electronic states which
emerge from the ground state and the first excited states of the
reactants. Our main goal is analyzing the electronic factors which
could be important in the competition between the channels lead-
ing to the C–H and C–F oxidative addition of the fluorocarbon mol-
ecule to the atomic cation.
Likewise, in order to gain some insight on the factors which
determine the preference of this reaction toward the product
of the CH3F addition and not to the fluorine abstraction product
M–F+ detected for the reaction of fluoromethane with most of
the early transition metal ions [9], the energy of the asymptotic
limit involving the radical species Ru–F+ + CH3 was also
investigated.
2. Computational details
CASSCF–MRMP2 calculations were carried out to obtain the po-
tential energy curves for representative electronic states which
correlate with the ground state and the two low-lying excited
states of the reactants Ru+(4F, 6D, 2D) + CH3F. Three approaching
modes of the metal ion toward the fluorocarbon molecule were
investigated (Scheme 1): the linear approach of Ru+ to the fluorine
atom along the C–F axis of the CH3F molecule and the insertion of
the ion into both the C–H and C–F bonds of the fluorinated mole-
cule. For the linear interaction only electronic states belonging to
the Cs symmetry group were investigated. Potential energy curves
for the states arising from this approach were built performing
geometry optimization calculations at selected values of the Ru–F
distance in the interval 1.5–6 Å, keeping fixed the C–F–Ru angle
at 180°.
Potential energy curves for the electronic states which evolve
from the insertion of the metal cation into the C–H and C–F bonds

0009-2614/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2009.05.038
 E. Bernabé et al. / Chemical Physics Letters 475 (2009) 188–192 189

16 electrons in 10 orbitals. This active space includes most of the

C F Ru 21 valence electrons and it was kept fixed throughout all points
along the different potential energy curves. In all the cases, the s
orbital and the six-Cartesian d orbitals of the transition ion were
I used to form the active space. For insertion of the cation into the
C–H bond, the s-type functions of the carbon and hydrogen atoms
F as well as a p function of the fluorine atom were also included in
C H C H C F the active space. Likewise, for C–F bond activation reactions the
H p-type functions of the fluorine atom were added in the active
F H
space.
Ru Ru Ru
For MRMP2 calculations the CASSCF active orbitals were used as
II III IV the active space. All the calculations were performed using the
quantum chemistry code GAMESS [21].
Scheme 1.

of the fluorinated molecule were obtained from geometry optimi- 3. Results and discussion
zation calculations performed at selected values of the C–Ru–H or
C–Ru–F angles (each 10 degrees in the interval 0–180°). Oxidative In Fig. 1 are shown the potential energy curves for the electronic
addition of the C–H bond to Ru+ was analyzed for electronic states states which arise from the approach of the ruthenium ion to flu-
belonging to both C1 and Cs symmetry groups. Main difference be- oromethane along the C–F axis of the fluorocarbon molecule. Val-
tween these states is the neighbor atom, H or F, contained in the ues for the energy and some geometrical parameters at the energy
plane in which the insertion of the metallic ion into the C–H bond minima are provided in Table 1. As it is shown in this table, no sig-
takes place. nificant changes are obtained between CASSCF and MRMP2 energy
For both C–H and C–F insertion types, full geometry optimiza- values for the quadruplet and doublet electronic states. However,
tion calculations were performed at the located energy minima inclusion of the dynamical correlation modifies substantially en-
for the inserted species CH2F–Ru–H+ and CH3–Ru–F+. Stationary ergy values for the sextuplet electronic states. Differences between
points at all the potential energy curves corresponding to elec- CASSCF energy values and those evolving form higher level theory
tronic states which emerge from the linear approach of the reac- calculations, such as the MRMP2 energies reported in this contri-
tants and the insertion of the metallic cation into the C–F bond bution, usually appear in interactions which involve transition
of the methyl fluoride molecule were characterized as energy min- metal atoms or cations, thus stressing the importance of the elec-
ima or transition structures through normal mode analyses per- tron correlation effects in this kind of systems. For instance, Nakao
formed at CASSCF level. Stability of the stationary points on the et al. have analyzed the low-lying electronic states which emerge
potential energy curves belonging to the electronic states which from the reactions M+(Sc, Ni, Cu) + NH3 (mainly the singlet and
arise from the oxidative addition of the C–H bond of the fluorinated triplet states) determining also significant variations in the effect
molecule to the cation was not verified, due mainly to the high of the dynamical correlation on electronic states of different mul-
repulsive character exhibited by these channels (as discussed in tiplicity [22].
Section 3). Potential energy curves for all the electronic states investigated
It is pointed out that the methodological treatment followed for exhibit potential wells at values of the Ru–F distance near 2.5 Å.
calculating the potential energy curves implicitly takes into Energy minima for the electronic states correlating with the
account the possibility of occurrence of avoided crossings between
curves belonging to states of the same symmetry, as for each value
of the geometrical parameters, i.e. the Ru–F distance for the linear
states or the C–Ru–F and the C–Ru–H angles for the cation inser-
tion curves, it is determined the lowest-lying electronic state at
CASSCF level. Thus, potential energy curves are building taking into
account the energy values corresponding to these electronic states
(diabatic-like curves) and not those associated with only one elec-
tronic state arising from a specific configuration. Whereas at some
regions of the potential curves, mainly those corresponding to the
dissociated fragments and the energy barriers, it was required
averaging different electronic states in order to achieve the conver-
gence of the multiconfigurational functions, for most of the energy
minima it was found that the CASSCF expansion is dominated by
only one electronic configuration.
For ruthenium the Averaged Relativistic Effective Potential
(AREP) and the triple-f quality Gaussian basis set for the outer d
and s shells as given by LaJohn et al. were used [17]. The empty
5p shell was described by a double-f contraction of the three
Gaussian functions included in this basis set. Carbon and fluorine
atoms were described using the AREPs and the triple-f basis sets
for the 2s and 2p region provided by Pacios et al. [18,19]. These ba-
sis sets were augmented with a set of six-Cartesian d polarization
functions with exponents 0.626 (carbon) and 1.75 (fluorine). For
Fig. 1. Plot of the potential energy vs the Ru–F distance for the electronic states
hydrogen atoms the standard 6-31++G** basis set was used [20]. emerging from the linear approach of the metal cation to the fluorine atom of the
For all the reaction channels investigated, CASSCF calculations CH3F molecule. The C–F–Ru angle was kept fixed at 180°. Energies are relative to the
were performed taking into account an active space consisting of ground state dissociation limit Ru+(4F; 4d7) + CH3F.
190 E. Bernabé et al. / Chemical Physics Letters 475 (2009) 188–192

Table 1 0
Table 2
CASSCF and MRMP2 energies (kcal/mol) as well as some geometrical parameters (Å A) MRMP2 energies (kcal/mol) for the electronic states evolving from the insertion of the
+
for the linear electronic states which evolve from the direct approach of Ru to the ruthenium cation into the C–F bond of the methyl fluoride molecule.a
fluorine atom of the methyl fluoride molecule (\C—F—Ru ¼ 180 ).a
State Local minimum Energy barrier Energy minimum
State Energy Distance 4
A0 18.9 14.3 25.3
6 0
CASSCF MRMP2 Ru–F C–F A 10.6 20.1 20.9
2 0
4 A 7.0 29.3 10.5
A0 16.9 17.4 2.42 1.43 4 00
6 0 A 21.6 11.6 26.9
A 18.9 8.7 2.43 1.44 6 00
2 0 A 15.1 21.5 5.6
A 13.3 10.4 2.50 1.46 2 00
4 00 A 6.8 40.9 17.7
A 17.8 18.4 2.39 1.43
6 00
A 18.9 8.7 2.44 1.44 a
Energies are relative to the ground state dissociation limit Ru+(4F; 4d7) + CH3F.
2 00
A 13.3 10.3 2.50 1.46
a
Energies are relative to the ground state dissociation limit Ru+(4F; 4d7) + CH3F.
Table 3
Geometrical parameters (deg and Å) corresponding to the low-lying electronic states
ground quadruplet state and the first excited sextuplet state of the which emerge from insertion of the metallic ion into the C–F bond of the CH3F
molecule.
separated fragments lye below the ground state dissociation limit.
There are not significant variations in the geometrical parameters CH3RuF+ F–Ru–C angle Distance
of the fluorocarbon fragment at these energy minima with regard Ru–F Ru–C C–F
to the isolated molecule, so it is inferred that these potential wells 4
A0 117.6 1.79 1.95 3.20
arise from the electrostatic interaction between the reactants. In 6 0
A 137.1 1.84 1.96 3.54
2 0
this sense, the electronic states evolving from this approach do A 126.2 1.77 1.91 3.29
4 00
not represent viable channels for the activation of the C–F bond A 110.8 1.77 1.95 3.07
6 00
A 176.5 1.79 2.47 4.26
of fluoromethane (values for the C–F distance shown in Table 1 2 00
A 137.4 1.74 1.09 3.40
are only slightly different
0
than the calculated for the isolated
CH3F molecule, 1.42 Å A).
In Fig. 2 are shown the potential energy curves belonging to the
electronic states which emerge from the insertion of Ru+ into the fluorinated molecule at this potential well, thus suggesting that
C–F bond of the methyl fluoride. Energies at selected points of the formed adduct CH3F–Ru+ is stabilized by an electrostatic inter-
these reaction channels as well as some geometrical parameters action. The second energy minimum corresponds to the product of
at the energy minima corresponding to the inserted species CH3– the oxidative addition of the C–F bond to the metallic cation. The
Ru–F+ are collected in Tables 2 and 3. Potential energy curve for inserted specie CH3Ru–F+ is reached after surmounting a barrier
the electronic state 4A00 correlating with the ground state of the which is 11.6 kcal/mol above the ground state reference and it lies
reactants exhibits two energy minima. One potential well lies 26.9 kcal/mol below this limit. The 4A00 channel leads to the most
21.6 kcal/mol below the ground state of the fragments and it ap- stable product for the C–F oxidative addition reaction. In accord
pears at small F–Ru–C angles, when the reactants approach each with data in Table 2 the potential well for this electronic state is
other. As for the linear electronic states discussed before, no signif- located at an F–Ru–C angle of 110.8° and a C–F distance of 3.07 Å
icant changes are detected in the geometrical parameters of the (more than twice the value of the equilibrium distance in the
fluoromethane molecule). Although forming a slightly less stable
product, the electronic state 4A0 exhibits a similar behavior. In fact,
the potential energy curves corresponding to the remainder
electronic states also show a similar shape and all of them exhibit
potential wells lying below the ground state of the fragments for
the product evolving from the C–F oxidative addition. The favor-
able trend to form stable products followed by the electronic chan-
nels correlating with the two excited states of the reactants could
be relevant in the context of the spectrometric studies made by
Zhao et al. on the Ru+ + CH3F reaction, as important contribution
of excited states to the total population (50% or above) was esti-
mated for the cation in these experimental determinations [9].
All the investigated channels for the insertion of the metal ion
into the C–F bond of the fluorocarbon compound exhibit an impor-
tant stabilization of the adduct CH3F–Ru+ (in fact, for the 6A00 elec-
tronic state, the adduct arising from the electrostatic attraction
between the fragments is more stable than the inserted product).
For each of these channels, the energy barrier separating the elec-
trostatic adduct and the C–F oxidative addition product CH3–Ru–F+
could prevent the insertion product be reached (for quadruplet and
sextuplet electronic states the height of the energy barrier is above
30 kcal/mol). In this line, it is important pointing out that the pro-
cedure followed for studying this reaction experimentally could
play an important role in determining the adduct or insertion
product obtained from these reaction channels. The electrostatic
interactions favoring the stabilization of the adduct at the initial
Fig. 2. Potential energy curves for the electronic states which arise from the
stage of the reaction probably are not so relevant in the context
insertion of Ru+ into the C–F bond of methyl fluoride. Energies are relative to the of experimental determinations performed through mass spectro-
ground state dissociation limit Ru+(4F; 4d7) + CH3F. metric techniques, due mainly to the expected adduct destabiliza-
 E. Bernabé et al. / Chemical Physics Letters 475 (2009) 188–192 191

tion and the subsequent lowering of the energy barrier which must
be surmounted to reach the insertion product. Thus, in our opinion,
the product detected by spectrometric determinations made on
this reaction, such as that reported in Ref. [9], would correspond
to the inserted specie CH3–Ru–F+.
Potential energy curves for the electronic states which evolve
from the insertion of Ru+ into the C–H bond of fluoromethane
are shown in Fig. 3. Main difference between channels belonging
to C1 and Cs symmetry groups is the H or F atom lying in the plane
in which insertion of the cation into the C–H bond takes place. The
electronic states belonging to the Cs symmetry group exhibit an
energy minimum at the initial stage of the reaction. In the same
way as for the channels leading to the C–F bond activation dis-
cussed before, these energy minima appear mainly as consequence
of the electrostatic interaction between the positive ion and the
fluorine atom; no significant variations in the geometrical param-
eters of the fluorocarbon molecule are detected at these potential
wells. Once the initial stage of the reaction is overcome, the poten-
tial energy curves for states belonging to both symmetry groups
behave in a similar way. Neither of the reaction channels investi-

Fig. 3. Potential energy curves for the low-lying electronic states which evolve from the insertion of Ru+ into the C–H bond of the CH3F molecule. Plots for electronic states
belonging to both Cs and C1 symmetry groups are shown. Energies are relative to the ground state dissociation limit Ru+(4F; 4d7) + CH3F.

Fig. 4. Schematic representation of the mechanism for the C–F oxidative addition of CH3F to the Ru+ cation.
192 E. Bernabé et al. / Chemical Physics Letters 475 (2009) 188–192
gated for the insertion of the cation into the C–H bond of fluorom-
ethane leads to the formation of a stable product, so it is concluded
that the oxidative addition of the C–H bond to the ruthenium cat-
ion is not favored.
Thus, the picture obtained for the reaction Ru+ + CH3F in this
study is consistent with the available experimental data [9]. In fact,
it is proposed that the Ru+CH3F addition product detected in Ref.
[9] by mass spectrometry emerges selectively from the channels
leading to the C–F oxidative addition to the metal cation. In
Fig. 4 is shown a schematic representation of the mechanism fol-
lowed by this reaction when insertion of the metallic cation into
the C–F bond of the fluorinated molecule occurs through the low-
est energy path corresponding to the 4A00 channel which emerges
from the ground state of the reactants (Fig. 2).
In addition to the C–H and C–F oxidative addition channels dis-
cussed before, the energy for the asymptote involving the radical
species Ru–F+ + CH3 was calculated with the aim of analyzing the
factors which determine the preference of this reaction toward
the CH3F addition and not to the fluorine abstraction product
M–F+ detected for the reaction of the fluorocarbon compound with
most of the early transition metal ions [9]. The asymptotic limits
corresponding to the quadruplet and sextuplet channels lye
23.4 kcal/mol above the ground state of the reactants (roughly
50 kcal/mol above the global minimum corresponding to the most
stable electronic state 4A00 ). The less interesting doublet asymptote
is 50 kcal/mol above the ground state reference. The comparison
between the energy values for the products emerging from the
fluorine abstraction and the C–F oxidative addition channels
clearly favors the product obtained through the second reaction
channel. Interestingly, for the reaction La+ + CH3F, the energy value
obtained through DFT calculations for the asymptote La–F+ + CH3 is
41.2 kcal/mol below the ground state of the reactants [13]. This
energy value is consistent with the abstraction products experi-
mentally observed for that reaction [9]. Thus, the comparison of
the value in Ref. [13] for the asymptote leading to the fluorine
abstraction by La+ and the reported here for the corresponding
reaction with Ru+ seems to support the thermodynamic control
proposed in Ref. [9] for the fluorine abstraction reactions
M+ + CH3F ? M–F+ + CH3. For this kind of reactions, the energy dif-
ference between the asymptotes corresponding to the reactants
and products must depend strongly on the stability of the specie
M–F+.
4. Conclusions
Potential energy curves for the channels evolving from the low-
lying electronic states of the reactants have been analyzed for the
reaction Ru+ + CH3F. Favorable channels leading to stable products
were detected for the insertion of the metal ion into the C–F bond
of the fluorocarbon compound. In accord with the results evolving
from this study, CH3F addition to the metal cation does not occur
through channels involving C–H oxidative addition. Likewise, the
comparison between the energy values for the products emerging
from the fluorine abstraction and the C–F oxidative addition chan-
nels clearly favors the product obtained from the insertion of the
metal cation into the C–F bond of the fluorinated molecule.
Acknowledgements
This research was supported by the Universidad Nacional Autó-
noma de México (DGAPA-IN105007) and El Consejo Nacional de
Ciencia y Tecnología (CONACYT-52309).
References
[1] J.L. Kiplinger, T.G. Richmond, C.E. Osterberg, Chem. Rev. 94 (1994) 373.
[2] R.N. Perutz, T. Braun, in: R.H. Crabtree, D.M.P. Mingos (Eds.), Comprehensive
Organometallic Chemistry III, vol. 1, Elsevier, Amsterdam, 2007, p. 725.
[3] Q. Chen, B.S. Freiser, J. Phys. Chem. A 102 (1998) 3343.
[4] R. Bosque et al., J. Am. Chem. Soc. 120 (1998) 12634.
[5] M. Jakt, L. Johannissen, H.S. Rzepa, D.A. Widdowson, R. Wilhelm, J. Chem. Soc.,
Perkin Trans. (2002) 576.
[6] H. Gerard, E.R. Davidson, O. Eisenstein, Mol. Phys. 100 (2002) 533.
[7] M. Reinhold, J.E. McGrady, R.N. Perutz, J. Am. Chem. Soc. 126 (2004) 5268.
[8] H. Torrens, Coord. Chem. Rev. 249 (2005) 1957.
[9] X. Zhao, G.K. Koyanagi, D.K. Bohme, J. Phys. Chem A. 110 (2006) 10607.
[10] E.D. Smurnyi, I.P. Gloriozov, Y.A. Ustynyuk, Russ. J. Phys. Chem. 77 (2003)
1699.
[11] G.Th. de Jong, F.M. Bickelhaupt, J. Phys. Chem. A 109 (2005) 9685.
[12] F. Colmenares, H. Torrens, J. Phys. Chem. A 109 (2005) 10587.
[13] Y.C. Wang, Z.Y. Liu, Z.Y. Geng, X.Y. Yang, L.G. Gao, X.X. Chen, J. Mol. Struct.
(Theochem.) 765 (2006) 27.
[14] D. Zhang, C. Zhang, C. Liu, J. Organomet. Chem. 640 (2001) 121.
[15] X. Zhao, A.C. Hopkinson, D.K. Bohme, Chem. Phys. Chem. 9 (2008) 873.
[16] T.H. Li, C.M. Wang, S.W. Yu, X.Y. Liu, X.H. Li, X.G. Xie, Chem. Phys. Lett. 463
(2008) 334.
[17] L.A. LaJohn, P.A. Christiansen, R.B. Ross, T. Atashroo, W.C. Ermler, J. Chem. Phys.
87 (1987) 2812.
[18] L.F. Pacios, P.C. Gómez, Int. J. Quantum Chem. 49 (1994) 817.
[19] L.F. Pacios, P.A. Christiansen, J. Chem. Phys. 82 (1985) 2664.
[20] Basis set was obtained from the Extensible Computational Chemistry
Environment Basis Set Database, Version 02/25/04, as developed and
distributed by the Molecular Science Computing Facility, Environmental and
Molecular Sciences Laboratory which is part of the Pacific Northwest
Laboratory, P.O. Box 999, Richland, Washington 99352, USA, and funded by
the U.S. Department of Energy. The Pacific Northwest Laboratory is a multi-
program laboratory operated by Battelle Memorial Institute for the U.S.
Department of Energy under contract DE-AC06-76RLO 1830. Contact Karen
Schuchardt for further information.
[21] M.W. Schmidt et al., J. Comput. Chem. 14 (1993) 1347.
[22] Y. Nakao, T. Taketsugu, K. Hirao, J. Chem. Phys. 110 (1999) 10863.