J. Am. Chem. Soc.

2000, 122, 3867-3877 3867

Theoretical Study of Ruthenium-Catalyzed Hydrogenation of Carbon

Dioxide into Formic Acid. Reaction Mechanism Involving a New
Type of σ-Bond Metathesis
Yasuo Musashi*,† and Shigeyoshi Sakaki*,‡
Contribution from the Information Processing Center, Kumamoto UniVersity, Kumamoto 860-8555, Japan,
and Department of Applied Chemistry and Biochemistry, Faculty of Engineering, Kumamoto UniVersity,
Kumamoto 860-8555, Japan
ReceiVed October 25, 1999

Abstract: Ruthenium-catalyzed hydrogenation of CO2 into formic acid was theoretically investigated with
the DFT(B3LYP) method, where cis-RuH2(PH3)4 was adopted as a catalyst model. Theoretical calculations
show that (1) CO2 insertion into the Ru-H bond occurs with an activation energy (Ea) of 29.3 kcal/mol in
cis-RuH2(PH3)4 and with an Ea value of 10.3 kcal/mol in cis-RuH2(PH3)3; (2) six-membered σ-bond metathesis
of RuH(η1-OCOH)(PH3)3(H2) occurs with a much smaller Ea value (8.2 kcal/mol) than four-membered σ-bond
metathesis (Ea ) 24.8 kcal/mol) and five-membered H-OCOH reductive elimination (Ea ) 25.5 kcal/mol);
(3) three-membered H-OCOH reductive elimination requires a very much larger Ea value of 43.2 kcal/mol;
(4) if PH3 dissociates from cis-RuH2(PH3)4, the CO2 hydrogenation takes place through the CO2 insertion into
the Ru-H bond of RuH2(PH3)3 followed by the six-membered σ-bond metathesis, where the rate-determining
step is the CO2 insertion; and (5) if PH3 does not dissociate from cis-RuH2(PH3)4 and cis-RuH(η1-OCOH)-
(PH3)4, the CO2 hydrogenation proceeds through the CO2 insertion into the Ru-H bond of cis-RuH2(PH3)4
followed by the H-OCOH reductive elimination, where the rate-determining step is the CO2 insertion. From
the above conclusions, one might predict that (1) excess phosphine suppresses the reaction, (2) the use of
solvent that facilitates phosphine dissociation is recommended, and (3) the ruthenium(II) complex with three
phosphine ligands is expected to be a good catalyst. The electronic processes and characteristic features of the
CO2 insertion reaction and the σ-bond metathesis are discussed in detail.

1. Introduction [RhH2(PMe2Ph)3(L)]+ and spectroscopically detected Rh(III) η1-

formate and Rh(III) η2-formate complexes.9 From these results,
CO2 fixation is an important subject of research in organo-
they proposed that the reaction proceeded through CO2 insertion
metallic and catalytic chemistries.1 One of the most attractive
into the Rh(III)-H bond of [RhH2(PMe2Ph)3(L)]+ followed by
and interesting reactions of CO2 fixation is transition metal
reductive elimination of formic acid from [RhH(η1-OCOH)(PMe2-
catalyzed CO2 hydrogenation into formic acid,2-6 because
Ph)3(L)]+ (L ) solvent). Also, Leitner found that the Rh(I)
formic acid is often used as a raw material in organic syntheses.
hydride complex, RhH(P-P), catalyzed the hydrogenation of CO2
Such transition metal complexes as [WH(CO)5]-,7 RhH(P-P)2
into formic acid.8 Later, Hutschka et al. experimentally and
(P-P ) 1,2-bis(diphenylphosphino)ethane or 1,3-bis(diphe-
theoretically investigated this catalytic reaction in detail and
nylphosphino)propane),8 [RhH2(PMe2Ph)3(L)]+ (L ) H2O or
proposed that this reaction took place through the CO2 insertion
THF),9 and cis-RuH2(PR3)4 (R ) Me10 or Ph11) were used as
into the Rh(I)-H bond of RhH(PH3)2 followed by the σ-bond
catalysts of this reaction. Tsai and Nicholas experimentally
metathesis of Rh(η1-OCOH)(PH3)2 with molecular hydrogen.12
investigated a hydrogenation reaction of CO2 catalyzed by
Recently, Jessop, Ikariya, and Noyori succeeded in significantly
† Information Processing Center. efficient hydrogenation of CO2 into formic acid with Ru(II)
‡ Department of Applied Chemistry and Biochemistry, Faculty of complexes in supercritical CO2 (eq 1).10 The extremely high
Engineering.
(1) Behr, A. Carbon Dioxide ActiVation by Metal Complex; VCH cis-RuH2(PMe3)4
Publishers: Weinheim, Germany, 1988.
(2) Jessop, P. G.; Morris, R. H. Coord. Chem. ReV. 1992, 121, 155.
CO2 + H2 9
in scCO , N(C H )
8 HCO2H (1)
2 2 5 3
(3) Jessop, P. G.; Ikariya, T.; Noyori, R. Chem. ReV. 1995, 95, 259.
(4) (a) Leitner, W. Angew. Chem., Int. Ed. Engl. 1995, 34, 2207. (b) catalytic activity of the Ru(II) complex motivates us to
Leitner, W. Coord. Chem. ReV. 1996, 153, 257.
(5) Komiya, H.; Yoshida, Y.; Hirai, H. Chem. Lett. 1975, 1223. investigate theoretically the Ru-catalyzed hydrogenation of CO2
(6) Kröcher, O.; Köppel, R. A.; Baiker, A.Chem. Commun. 1997, 453. into formic acid, since it is considerably interesting and
(7) Darensbourg, D. J.; Ovalles, C. J. Am. Chem. Soc. 1984, 106, 3750. important to clarify the reaction mechanism and the rate-
(8) Burgemeister, T.; Kastner, F.; Leitner, W. Angew. Chem., Int. Ed.
Engl. 1993, 22, 739. determining step of Ru(II)-catalyzed hydrogenation of CO2.
(9) Tsai, J.-C.; Nicholas, K. M. J. Am. Chem. Soc. 1992, 114, 5117. In the present work, all the elementary steps involved in the
(10) (a) Jessop, P. G.; Ikariya, T.; Noyori, R. Nature 1994, 368, 231. catalytic cycle of Ru(II)-catalyzed hydrogenation of CO2 into
(b) Jessop, P. G.; Ikariya, T.; Noyori, R. Science 1995, 269, 1065. (c) Jessop,
P. G.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 344. (12) (a) Hutschka, F.; Dedieu, A.; Eichberger, M.; Fornika, R.; Leitner,
(11) Inoue, Y.; Izumida, H.; Sasaki, Y.; Hashimoto, H. Chem. Lett. 1976, W. J. Am. Chem. Soc. 1997, 119, 4432. (b) Hutschka, F.; Dedieu, A. J.
863. Chem. Soc., Dalton Trans. 1997, 1899.

10.1021/ja9938027 CCC: $19.00 © 2000 American Chemical Society

Published on Web 04/08/2000
3868 J. Am. Chem. Soc., Vol. 122, No. 16, 2000 Musashi and Sakaki

formic acid are theoretically investigated with the density species must be reproduced through the oxidative addition of
functional theory (DFT) method. Our purposes here are (1) to H2 to a Ru(0) complex, Ru(PH3)n(HCOOH) or Ru(PH3)n (eqs
elucidate the reaction mechanism, (2) to show what is the rate- 4 and 5). The other is the σ-bond metathesis of RuH(η1-OCOH)-
determining step, and (3) to provide detailed knowledge of (PH3)n with a hydrogen molecule (eqs 6a and 6b). To perform
characteristic features of this reaction. Our intention here is to the σ-bond metathesis, H2 must coordinate with Ru. When n )
present a clear conclusion of the reaction mechanism and to 4, RuH(η1-OCOH)(PH3)4 possesses no room for H2 coordina-
indicate the importance of six-membered σ-bond metathesis of tion, and therefore, substitution of H2 for PH3 must occur to
RuH(η1-OCOH)(PH3)n (n ) 3 or 4) with H2. This six-membered yield RuH(η1-OCOH)(PH3)3(H2), as shown in eq 6a. When n
σ-bond metathesis is significantly different from the four- ) 3, RuH(η1-OCOH)(PH3)3 has an unoccupied coordination site,
membered σ-bond metathesis proposed recently,12 but similar and therefore, H2 easily coordinates with Ru to afford RuH-
to formate-assisted six-membered H2 splitting which was (η1-OCOH)(PH3)3(H2), as shown in eq 6b. We investigated here
previously proposed by Darensbourg et al.7 in the hydrogenation six-membered σ-bond metathesis and four-membered σ-bond
of CO2 into formic acid catalyzed by [WH(CO)5]- but has metathesis in RuH(η1-OCOH)(PH3)3(H2). When the σ-bond
received little attention so far. Similar H2 splitting assisted by metathesis takes place, the active species of cis-RuH2(PH3)3 is
a ligand has also been reported by Morris et al.,13 Crabtree et
produced concomitantly with the formation of HCOOH, and
al.,14 and Milet et al.15
therefore, the oxidative addition of H2 to a Ru(0) complex does
2. Catalyst Model and Examined Reactions not need to occur.

Since a ruthenium(II) complex, RuH2(PMe3)4, was used as a

catalyst in Ru(II)-catalyzed hydrogenation of CO2 into formic 3. Computations
acid,10 we adopted here cis-RuH2(PH3)4 as a catalyst model.
The density functional theory (DFT) method20 was employed here
Komiya et al.16 and Kolomnikov et al.17 experimentally reported with the B3LYP functional for the exchange correlation term.21,22
that the CO2 insertion into the Ru-H bond of cis-RuH2(PR3)4 Geometries were optimized with the following basis set system (BS-
(1) occurred with phosphine dissociation when PPh3 was used I): core electrons of P (up to 2p) and Ru (up to 3d) were replaced
as a ligand. On the other hand, Jessop et al. reported that addition with effective core potentials (ECPs), and their valence electrons were
of PMe3 did not suppress the stoichiometric CO2 insertion in represented with (21/21/1) and (311/311/211) sets, respectively.23,24
cis-RuH2(PMe3)4.10c This result suggests that CO2 is inserted MIDI-4 sets25 were employed for C and O, and a (4s)/[2s] set26 was
into the Ru-H bond without PMe3 dissociation. Several reports used for H. A d-polarization function25 was added on C and O, and a
suggested that a bulky phosphine tends to dissociate from the p-polarization function26 was added on the active hydrogen atom that
central metal.18 Thus, we investigated two types of CO2 was hydride and the H atom of formate. Energy changes27 were
insertion; one is the CO2 insertion into the Ru-H bond of a calculated with a better basis set system (BS-II), using DFT(B3LYP)/
six-coordinate Ru(II) complex, cis-RuH2(PH3)4 (1a) (eq 2a), BS-I optimized geometries. In BS-II, a (541/541/211)28 set was
without PH3 dissociation, and the other is the CO2 insertion employed for Ru with the same ECPs as those in BS-I.24 A MIDI-4
into the Ru-H bond of a five-coordinate Ru(II) complex, cis- set25 was used for P, where a d-polarization function was added.25 For
RuH2(PH3)3 (1b) (eq 2b), with PH3 dissociation. C and O, (9s 5p 1d)/[3s 2p 1d] sets26 were used with a p-diffuse
function.26 For the active H atom, a (5s 1p)/[3s 1p] set29 was employed.
cis-RuH2(PH3)4 + CO2 f RuH(η1-OCOH)(PH3)4 (2a)
(13) (a) Park, S.; Ramachandran, R.; Lough, A. J.; Morris, R. H. J. Chem.
Soc., Chem. Commun. 1994, 2201. (b) Lough, A. J.; Park, S.; Ramachandran,
cis-RuH2(PH3)3 + CO2 f RuH(η -OCOH)(PH3)3
1
(2b) R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356.
(14) (a) Lee, J. C., Jr.; Rheingold, A. L.; Muller, B.; Pregosin, P. S.;
RuH(η1-OCOH)(PH3)n f Ru(PH3)n(HCOOH) or Crabtree, R. H. J. Chem. Soc., Chem. Comm. 1994, 1021. (b) Lee, J. C.,
Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994,
(n ) 3 or 4) 116, 11014. (c) Crabtree, R. H.; Siegbahn, P. E. M.; Eisenstein, O.;
Ru(PH3)4 + HCOOH (3) Rheingold, A. L.; Koetzle, T. F. Acc. Chem. Res. 1996, 29, 348.
(15) (a) Milet, A.; Dedieu, A.; Kapteijn, G.; van Koten, G. Inorg. Chem.
1997, 36, 3223. (b) Milet, A.; Dedieu, A.; Canty, A. J. Organometallics
Ru(PH3)4(HCOOH) + H2 f 1997, 16, 5331.
cis-RuH2(PH3)4 + HCOOH (4) (16) (a) Komiya, S.; Yamamoto, A. J. Organomet. Chem. 1972, 46, C58.
(b) Komiya, S.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1976, 49, 784.
(17) Kolomnikov, I. S.; Gusev, A. I.; Aleksandrov, G. G.; Lobeeva, T.
Ru(PH3)4 + H2 f cis-RuH2(PH3)4 (5) S.; Struchkov, Yu. T.; Vol’pin, M. E. J. Organomet. Chem. 1973, 59, 349.
(18) (a) Tolman, C. A. Chem. ReV. 1977, 77, 313. (b) Yamamoto, A.
RuH(η1-OCOH)(PH3)4 + H2 f Organotransition Metal Chemistry; John Wiley & Sons Inc.: New York,
1986; Chapter 6, pp 195-304 and references therein. (c) Collman, J. P.;
cis-RuH(η1-OCOH)(PH3)3(H2) + PH3 Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of
Oragnotransition Metal Chemistry; University Science Books: Mill Valley,
f RuH2(PH3)3(HCOOH) + PH3 (6a)19 CA, 1987; Chapter 3, pp 57-234 and references therein.
(19) The term “cis” represents here that the H2 ligand takes a position
cis to the η1-OCOH ligand.
RuH(η1-OCOH)(PH3)3 + H2 f (20) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and
Molecules; Oxford University Press: New York, 1989.
cis-RuH(η1-OCOH)(PH3)3(H2) (21) (a) Becke, A. D. Phys. ReV. A 1988, 38, 3098. (b) Becke, A. D. J.
Chem. Phys. 1993, 98, 1372. (c) Becke, A. D. J. Chem. Phys. 1993, 98,
f RuH2(PH3)3(HCOOH) (6b)19 5648.
(22) Lee, C.; Yang, W.; Parr, R. G. Phys. ReV. B 1988, 37, 785.
(23) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
Two reaction courses are considered possible in the formation (24) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.
of formic acid from a formate complex, RuH(η1-OCOH)(PH3)n (25) Huzinaga, S.; Andzelm, J.; Klobukowski, M.; Radzio-Andzelm, E.;
(n ) 3 or 4); one is the reductive elimination of formic acid Sakai, Y.; Tatewaki, H. Gaussian Basis Sets for Molecular Calculations;
Elsevier: Amsterdam, 1984.
from RuH(η1-OCOH)(PH3)n, to yield Ru(PH3)n(HCOOH) (eq (26) Dunning, T. H.; Hay, P. J. In Methods of Electronic Structure
3). In this case, the ruthenium dihydride complex of an active Theory; Schaefer, H. F., Ed.; Plenum: New York, 1977; p 1.
Ru-Catalyzed Hydrogenation of CO2 into HCO2H J. Am. Chem. Soc., Vol. 122, No. 16, 2000 3869

Figure 1. Geometry changes in the insertion of CO2 into the Ru-H bond of cis-RuH2(PH3)n (n ) 3 and 4). Bond distances are in angstroms and
bond angles in degrees. In parentheses are the energy differences from 1a (kcal/mol; DFT (B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation). The
P1H3 and P2H3 ligands, which are perpendicular to the P3-Rh-H1 plane, are omitted for brevity because the Ru-P1 and Ru-P2 distances hardly
change through the hydrogenation of CO2.

All the transition states were ascertained by vibrational frequency 4. Results and Discussion
calculation with the DFT(B3LYP)/BS-I method. Gaussian 94 and 98
programs were used in these calculations.30,31 4.1. The CO2 Insertion into the Ru-H Bond of RuH2-
(PH3)n (n ) 3 or 4). Geometry changes in the CO2 insertion
(27) The reaction energy of hydrogenation of carbon dioxide into formic reaction are shown in Figure 1. cis-RuH2(PH3)4 1a takes a six-
acid (H2 + CO2 f HCO2H) is calculated to be -5.4, -4.2, and -3.4 kcal/ coordinate pseudo-octahedral structure. The optimized Ru-H
mol with the DFT(B3LYP), MP4(SDQ), and CCSD(T) methods, respec- bond distance (1.615 Å) is within a range of experimental
tively, where the BS-II set was used. After correction of zero-point energy,
the reaction energy is 2.2, 3.4, and 4.2 kcal/mol for DFT(B3LYP), MP4- values: 1.630 Å in RuH(η5-C5H5)(PMe3)2 and 1.602 Å (average)
(SDQ), and CCSD(T) values, respectively, where the zero-point energy was in [RuH2(η5-C5H5)(PMe3)2]+.32 The similar Ru-H distance was
evaluated with the DFT(B3LYP) method. The G2 calculation provides the previously reported in a theoretical investigation of RuH2-
reaction energy of 5.4 kcal/mol at 0 K. These results indicate that the DFT-
(B3LYP)/BS-II calculation tends to underestimate the endothermicity and
(PH3)4.33 The Ru-P1 and Ru-P2 bonds are much longer than
that the zero-point energy correction increases the endothermicity. The zero- the Ru-P3 and Ru-P4 bonds because of the strong trans
point energy is large when a molecule involves C-H and O-H bonds influence of the hydride ligand (see Figure 1 for P1-P4).
because these bonds exhibit high vibrational frequency. Thus, the CO2
insertion would be slightly less exothermic and the H-OCOH reductive In the CO2 insertion reaction without PH3 dissociation, CO2
elimination would be slightly more endothermic than those calculated with approaches Ru to form a precursor complex, cis-RuH2(PH3)4-
the DFT(B3LYP)/BS-II method. However, this deviation would not change (CO2) 2a. In 2a, the Ru-H2 bond (1.633 Å) and the Ru-P4
the conclusion about reaction courses because of considerably large
differences in activation barrier between the four-membered σ-bond
bond (2.410 Å) are only 0.018 and 0.006 Å longer than those
metathesis and the six-membered σ-bond metathesis and between the six- of 1a, respectively, and the other moiety has almost the same
membered σ-bond metathesis and the five-membered H-OCOH reductive geometry as that of 1a. The CO2 moiety also little distorts. The
elimination. C-H2 distance (2.919 Å) and the Ru-O1 distance (4.522 Å)
(28) Couty, M.; Hall, M. B. J. Comput. Chem. 1996, 17, 1359.
(29) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. are quite long. Consistent with these features, the stabilization
J. Comput. Chem. 1983, 4, 294. energy by CO2 coordination is only 2.6 kcal/mol, as usually
(30) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; observed in the precursor complex of the CO2 insertion into
Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T. A.; Petersson,
G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, metal-hydride and metal-alkyl bonds.8,34
V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; In the transition state TS2a-3a, only one imaginary frequency
Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; of 413i cm-1 was calculated. The eigenvector with this
Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.;
Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head- imaginary frequency mainly involves the approach of O1 to Ru
Gordon, M.; Gonzalez, C.; Pople, J. A. GAUSSIAN 94, revision E2; Gaussian and the elimination of H2 from Ru (See Supporting Information).
Inc.: Pittsburgh, PA, 1995. These geometry changes are consistent with the CO2 insertion
(31) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.;
into the Ru-H bond. In TS2a-3a, the Ru-H2 bond considerably
Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. lengthens by 0.503 Å and the C-H2 distance shortens to 1.190
D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, Å, which is very close to the C-H bond of the formate anion.
M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Also, the OCO angle significantly bends and both C-O bonds
Ochterski, J.; Petterson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; considerably lengthen. These features indicate that the Ru-H2
Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi,
I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; (32) Brammer, L.; Klooster, W. T.; Lemke, F. R. Organometallics 1996,
Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. 15, 1721.
W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; (33) Macgregor, S. A.; Eisenstein, O.; Whittlesey, M. K.; Perutz, R. N.
Head-Gordon, M.; Replogle, E. S.; Pople, J. A. GAUSSIAN 98, revision J. Chem. Soc., Dalton Trans. 1998, 291.
A6; Gaussian Inc.: Pittsburgh, PA, 1998. (34) Musashi, Y.; Sakaki, S. J. Chem. Soc., Dalton Trans. 1998, 577.
3870 J. Am. Chem. Soc., Vol. 122, No. 16, 2000 Musashi and Sakaki

Figure 2. Geometry changes in the reductive elimination of formic acid from RuH(η1-OCOH)(PH3)4 3a. Bond distances are in angstroms and
bond angles in degrees. In parentheses are the energy differences from 3a (kcal/mol; DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation). The
PH3 ligands at a perpendicular position of the P3-Rh-H1 plane are omitted for brevity.

bond is much weakened and the formate anion has been almost a d6 electron configuration. The Ru-(η1-OCOH) moiety
formed at TS2a-3a. However, the Ru-O1 distance (2.802 Å) is resembles well that of 3a.
much longer than the usual Ru-formate bond, showing that From these results, it is clearly concluded that CO2 is inserted
the Ru-O1 bond has not been sufficiently formed. This is into the Ru-H bond with a large Ea value in cis-RuH2(PH3)4
because it is difficult for the Ru(II) complex to take a seven- but with a small Ea value in cis-RuH2(PH3)3.
coordinate structure and the Ru-O1 bond cannot be formed 4.2. Reductive Elimination of Formic Acid from RuH(η1-
without complete breaking of the Ru-H bond. As a result, a OCOH)(PH3)n (n ) 3 or 4). RuH(η1-OCOH)(PH3)4 3a and
significantly high activation barrier (Ea ) 29.3 kcal/mol) was RuH(η1-OCOH)(PH3)3 3b undergo the reductive elimination of
calculated, where the Ea value is defined as an energy difference formic acid (HCOOH), as shown in Figures 2 and 3, respec-
between TS2a-3a and 2a. tively. Starting from 3a, the reductive elimination takes place
The insertion product 3a is a monodentate formate complex through a three-membered transition state TS3a-6a to afford Ru-
which takes a six-coordinate pseudo-octahedral structure. Its (PH3)4 + HCOOH 6a. In TS3a-6a, only one imaginary frequency
Ru-O1 distance (2.127 Å) is shorter than the experimental value of 1118i cm-1 is calculated, and its eigenvector mainly involves
reported for RuH(η2-O2CH)(PPh3)3,17 probably because the Ru- the approach of H1 to O1. In this TS3a-6a, the Ru-O1 bond
O1 bond of the monodentate formate complex is stronger than considerably lengthens by 0.351 Å and the η1-formate ligand
that of the bidentate formate complex, RuH(η2-O2CH)(PPh3)3. significantly moves downward so that the O1 atom approaches
PH3 dissociation from cis-RuH2(PH3)4 occurs with a desta- the H1 atom. However, the Ru-H1 bond little lengthens and
bilization energy of 24.8 kcal/mol to yield cis-RuH2(PH3)3 1b. the O-H1 distance is still very long (1.673 Å). These features
Though this destabilization energy is somewhat large, a bulky indicate that the Ru-O1 bond much weakens but the Ru-H1
phosphine would dissociate from Ru(II) with a smaller desta- bond has not been broken yet, and the new O-H bond formation
bilization energy.18 CO2 coordinates with 1b, affording cis- has not been completed yet. In other words, the O1-H1 bond
RuH2(PH3)3(CO2) 2b with a stabilization energy of 4.6 kcal/ formation does not occur enough to compensate the energy
mol. In 2b, the Ru-O1 and C-H2 distances are rather long, destabilization by the Ru-O1 bond weakening. As a result, the
being 2.615 and 2.903 Å, respectively. These geometrical Ea value is very large (44.8 kcal/mol). In this reductive
features are similar to those of 2a. In 2b, CO2 is inserted into elimination, the product is considered to be Ru(PH3)4 +
the Ru-H bond through the transition state TS2b-3b, to yield a HCOOH 6a, since the Ru(0) complex tends to take a four-
monodentate formate complex, RuH(η1-OCOH)(PH3)3 3b. The coordinate structure. Further discussion of this reductive elimi-
eigenvector with an imaginary frequency (226i cm-1) exhibits nation is stopped here, because the reductive elimination more
geometry changes consistent with the CO2 insertion into the easily takes place via a different reaction course, as will be
Ru-H bond. The geometrical features of TS2b-3b resemble well discussed below.
those of TS2a-3a, except that the Ru-P3 and Ru-O1 bonds are The η1-formate complex 3a isomerizes to 4a by the rotation
significantly shorter than those of TS2a-3a. These shorter bonds of η1-formate about the C-O1 bond, as shown in Scheme 1. In
would arise from the lesser steric repulsion between CO2 and 4a, the O2 atom takes a position near the H1 atom (see Scheme
RuH2(PH3)3 in TS2b-3b than that in TS2a-3a. The activation 1 for O1, O2, and H1). This isomerization occurs via the transition
energy was calculated to be 10.3 kcal/mol, which is much state TS3a-4a. In TS3a-4a, only one imaginary frequency (164i
smaller than that for TS2a-3a. The insertion product 3b takes a cm-1) is calculated, and its eigenvector mainly involves the
five-coordinate square-pyramidal structure, since Ru(II) takes rotation of the O2CH2 moiety about the C-O1 bond. In this
Ru-Catalyzed Hydrogenation of CO2 into HCO2H J. Am. Chem. Soc., Vol. 122, No. 16, 2000 3871

Figure 3. Geometry changes in the reductive elimination of formic acid from RuH(η1-OCOH)(PH3)3 3b. Bond distances are in angstroms and
bond angles in degrees. In parentheses are the energy differences from 3b (kcal/mol; DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation). The
PH3 ligands at a perpendicular position of the P3-Rh-H1 plane are omitted for brevity.

Scheme 1 means that a Lewis base such as triethylamine is necessary to

release formic acid from Ru, as experimentally known.10
Starting from RuH(η1-OCOH)(PH3)3 3b, the reductive elimi-
nation of HCOOH also takes place through a three-membered
transition state TS3b-6b, as shown in Figure 3. In TS3b-6b, the
O1 atom slightly moves downward from the Ru(PH3)3 plane
and the H1 atom considerably moves toward the O1 atom. The
geometry of the Ru-O1-H1 moiety resembles well those of
TS3a-6a and TS4a-6a. Accordingly, the Ea value is very large
(39.8 kcal/mol).
transition state, the dihedral angle between the C-O2-H2 and
Also in 3b, the η1-formate ligand can rotate about the Ru-
the Ru-O1-C planes is about 90°, while the geometry of the
O1 bond, to yield the isomer 4b through the transition state
other part little changes. Consistent with the smalll geometry
TS3b-4b like the isomerization of 3a to 4a. The formate complex
changes, the isomerization easily occurs with a much smaller
4b undergoes the H-OCOH reductive elimination via either
Ea value of 6.6 kcal/mol.
three-membered TS4b-6b or five-membered TS4b-5b. TS4b-6b
From 4a, two types of reductive elimination are considered
resembles well TS3b-6b, and the Ea value is very large (40.4
to occur; one takes place through a three-membered transition
kcal/mol). However, TS4b-5b resembles TS4a-5a and the Ea value
state TS4a-6a which needs a considerably large Ea value of 43.2
is moderate (17.5 kcal/mol).
kcal/mol (the imaginary frequency of 1038i cm-1). In this
TS4a-6a, Ru-O1, O1-H1, and Ru-H distances are slightly In the three-membered reductive elimination, the product, Ru-
longer than those of TS3a-6a, while the geometry of the other (PH3)3 + HCOOH 6b, is less stable than TS4b-6b. This means
moiety is almost the same as that of TS3a-4a. The other type of that some product complex should exist between TS4b-6b and
reductive elimination proceeds through a five-membered transi- 6a. However, we omitted further examination, because this type
tion state TS4a-5a which needs a moderate Ea value of 25.5 kcal/ of reductive elimination is not favorable and the five-membered
mol (the imaginary frequency of 558i cm-1). TS4a-5a is reductive elimination occurs more easily. In the five-membered
considerably different from TS4a-6a, as follows: (1) the Ru- reductive elimination, the geometry of the product Ru(PH3)3-
O1 distance moderately lengthens by 0.12 Å, indicating that the (HCOOH) 5b is similar to that of TS4b-5b, and therefore, an
Ru-O1 bond has not been broken yet; (2) the O1 atom energy difference between TS4b-5b and 5b is very small (only
moderately moves downward; (3) the H1 atom moderately 0.4 kcal/mol). The HCOOH dissociation from 5b gives rise to
moves toward the O2 atom; and (4) the O2-H1 distance (1.152 a destabilization energy of 27.1 kcal/mol, to yield Ru(PH3)3 +
Å) is close to the normal O-H bond of HCOOH. These features HCOOH 6b, like 5a. These results again indicate that Lewis
indicate that the H-O bond is easily formed in this TS4a-5a base is necessary for this HCOOH dissociation.
with moderate geometry changes, unlike TS4a-6a. As a result, 4.3. Oxidative Addition of H2 to Ru(PH3)n (n ) 3 or 4).
the five-membered reductive elimination easily occurs through Ru(PH3)4 6a and Ru(PH3)3 6b do not have a hydride ligand.
TS4a-5a with a smaller Ea value than that of three-membered Thus, the oxidative addition of H2 to 6a and 6b (eq 5) must
reductive elimination. occur to form the active species cis-RuH2(PH3)n 1. We
The product, Ru(PH3)4(HCOOH) 5a, of this reductive elimi- investigated the H2 oxidative addition but failed to optimize
nation is a Ru(0) complex of HCOOH, which resembles well the geometry of the transition state. This reaction is significantly
the transition state TS4a-5a. Actually, 5a is slightly more stable exothermic; the exothermicity (Eexo) is 31.9 and 38.1 kcal/mol
than TS4a-5a by only 0.6 kcal/mol. The HCOOH dissociation for 1a and 1b, respectively. From these results, it is reasonably
from 5a causes destabilization in energy by ca. 7 kcal/mol. This concluded that the oxidative addition of H2 easily occurs with
3872 J. Am. Chem. Soc., Vol. 122, No. 16, 2000 Musashi and Sakaki

Figure 4. Geometry changes in the σ-bond metathesis of RuH(η1-OCOH)(PH3)3 with H2, in which H2 is at a position trans to H1. Bond distances
are in angstroms and bond angles in degrees. In parentheses are the energy differences from 3a (kcal/mol; DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I
calculation). See Figure 3 for TS3b-4b and 4b. The PH3 ligands at a perpendicular position of the P3-Rh-H1 plane are omitted for brevity.

no barrier. A similar result was theoretically reported in the involves the approach of Hβ to O1 but little involves the
oxidative addition of H2 to Ru(PH3)4.33 Moreover, the oxidative approach of HR to Ru. The HR-Hβ bond lengthens by 0.276 Å,
addition does not need to occur in the catalytic cycle, since the while the Ru-HR and O1-Hβ distances are much longer than
σ-bond metathesis of RuH(η1-OCOH)(PH3)n with H2 more the normal Ru-H and O-H bond distances, respectively,
easily occurs than the reductive elimination and the active showing that the new Ru-HR and O1-Hβ bonds have not been
species is reproduced through the σ-bond metathesis, as will completely formed at TS7a-8a. As a result, the Ea value is
be discussed below. Thus, we stopped further investigation of considerably large (24.8 kcal/mol). This four-membered σ-bond
this oxidative addition. metathesis is similar to the previously reported four-membered
4.4. σ-Bond Metathesis of RuH(η1-OCOH)(PH3)n (n ) 3 σ-bond metathesis of Rh(η1-OCOH)(PH3)2 with H212a and the
or 4) with H2. In the σ-bond metathesis of RuH(η1-OCOH)- H-H splitting by PdH(OH)(NH3).15a
(PH3)4 3a with H2, PH3 must be substituted for H2, to yield Isomerization of 7a to 7b easily proceeds via a transition state
RuH(η1-OCOH)(PH3)3(H2). We failed to optimize the transition TS7a-7b with a small activation barrier of only 3.4 kcal/mol (an
state of associative substitution of H2 for PH3, since one PH3 imaginary frequency of 167i cm-1). The σ-bond metathesis from
dissociated from Ru during the geometry optimization of the 7b also occurs through a four-membered transition state TS7b-8b
transition state. This result suggests that the associative substitu- with a very large Ea value of 29.3 kcal/mol (an imaginary
tion of H2 for PH3 would not occur, probably because 3a is frequency of 1184i cm-1).
coordinatively saturated and the seven-coordinate structure is The five-coordinate formate complex 4b, which is discussed
very unstable in the Ru(II) complex. Thus, the dissociative in Figure 3, also undergoes coordination of H2 to yield 7b, as
substitution of H2 for PH3 was investigated here. The PH3 shown in Figure 4. From 7b, the four-membered σ-bond
dissociation gives rise to a destabilization energy of 19.1 kcal/ metathesis might occur through TS7b-8b. However, this reaction
mol to afford a coordinatively unsaturated complex RuH(η1- needs a considerably large Ea value (see above and Figure 4).
OCOH)(PH3)3 3b (see Figure 4). This destabilization energy is Thus, the σ-bond metathesis starting from 4b is ruled out here.
smaller than the activation barrier of any reductive elimination Also, 7a isomerizes to 7c through a transition state TS7a-7c,
of H-OCOH from 3a, showing that the PH3 dissociation occurs which needs an Ea of 8.5 kcal/mol. From 7c, σ-bond metathesis
more easily than the H-OCOH reductive elimination. proceeds through a six-membered transition state TS7c-8c (Figure
H2 coordinates with 3b, to afford a molecular hydrogen 4). The eigenvector with the imaginary frequency (764i cm-1)
complex, RuH(η1-OCOH)(PH3)3(H2) 7a, with a stabilization mainly involves the approach of Hβ to O2 and that of HR to Ru.
energy of 7.6 kcal/mol. In 7a, the HR-Hβ bond distance (0.782 In TS7c-8c, the HR-Hβ and Ru-O1 distances lengthen by 0.290
Å) is slightly longer than the normal H-H bond (see Figure 4 and 0.066 Å, respectively, the Ru-HR distance shortens by
for HR and Hβ), and the geometry of the Ru(η1-OCOH)(PH3)3 0.117 Å, the Ru-H1 bond lengthens by 0.046 Å, and the O2-
moiety is almost the same as that of 3a, as shown in Figure 4. Hβ distance shortens to 1.183 Å. These geometrical changes
These features indicate that the HR-Hβ bond is little activated indicate that the HR-Hβ bond is considerably weakened and
by Ru and the coordinate bond of H2 is weak. Starting from the new Ru-HR and O2-Hβ bonds have been almost formed.
7a, the four-membered σ-bond metathesis takes place through The activation energy was calculated to be 8.2 kcal/mol, which
TS7a-8a which exhibits only one imaginary frequency of 1252i is much less than those of the four-membered metathesis and
cm-1. The eigenvector with the imaginary frequency mainly the three-membered and five-membered reductive eliminations.
Ru-Catalyzed Hydrogenation of CO2 into HCO2H J. Am. Chem. Soc., Vol. 122, No. 16, 2000 3873

Figure 5. Geometry changes in the σ-bond metathesis of RuH(η1-OCOH)(PH3)3 with H2, in which H2 is at a position cis to H1. Bond distances
are in angstroms and bond angles in degrees. In parentheses are the energy differences from 7a (kcal/mol; DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I
calculation). The PH3 ligands at a perpendicular position of the P3-Rh-H1 plane are omitted for brevity.

From these results, it should be concluded that the six-membered the σ-bond metathesis occurred in 7d (Figure 5) in which the
σ-bond metathesis is the easiest reaction path to afford formic η1-formate ligand is at a position trans to H1. Thus, we
acid. Darensbourg and Ovalles previously suggested that the investigated the isomerization of 7a to 7d followed by the
formation of formic acid might occur through either the formate- σ-bond metathesis of 7d, as shown in Figure 5. This isomer-
assisted heterolytic cleavage of H2 or the reductive elimination ization occurs via TS7a-7d with an Ea value of 17.7 kcal/mol.
of formic acids concomitant with the oxidative addition of H2 This isomerization corresponds to the associative substitution
to W.7 The former reaction is essentially the same as the six- of HR-Hβ for Hγ-Hδ. In TS7a-7d, the Hγ-Hδ moiety is much
membered σ-bond metathesis presented here. Also, Morris et distant from Ru and it does not seem to interact with Ru. Only
al.13 and Crabtree et al.14 experimentally proposed that the the approach of HR-Hβ to Ru is observed but the movement
ligand-assisted H-H splitting occurred through a six-membered of Hγ-Hδ is not observed in the eigenvector with imaginary
interaction, which is essentially the same as the present six- frequency (259i cm-1). In 7d, the HR-Hβ bond distance (0.868
membered σ-bond metathesis. Milet et al.15b also theoretically Å) is much longer, the Ru-H2 distance is much shorter, and
investigated the ligand-assisted H-H splitting through a mul- the Ru-O1 and Ru-H1 bonds are longer than those of 7a. These
timembered interaction which is similar to our six-membered features show that H2 more strongly and η1-formate less strongly
σ-bond metathesis. The geometry of the product complex RuH- coordinates with Ru, which is interpreted in terms of a strong
(PH3)3(HCOOH) 8c is similar to that of TS7c-8c. Consistent with trans influence of H1 in 7a and 7d. From 7d, the four-membered
this result, 8c is only 0.4 kcal/mol more stable than TS7c-8c
σ-bond metathesis occurs through TS7d-8d with an Ea value of
and less stable than 7c by 7.8 kcal/mol.35 Thus, the six-
16.3 kcal/mol. Also, 7d undergoes the isomerization followed
membered σ-bond metathesis via TS7c-8c is endothermic and
by either four-membered (TS7e-8e) or six-membered (TS7e-8f)
the reverse reaction easily occurs, which again indicates that
σ-bond metathesis with an Ea value of 21.9 or 0.5 kcal/mol,
Lewis base is necessary in the reaction.
respectively (see Figure 5). The Ea value for the 7d f 7e
In this σ-bond metathesis, the Ru-HR bond is formed at a
position trans to H1 (hydride). This geometry is unfavorable isomerization is also very small (2.4 kcal/mol). Though both
because of the strong trans influence of the H ligand. Actually, six-membered and four-membered σ-bond metatheses require
the Ru-HR bonds in TS7c-8c and 8c are much longer than the a lower Ea value than those of 7a as expected, the 7a f 7d
Ru-H bond of 3a. This unfavorable situation disappeared if isomerization requires a larger Ea value (17.7 kcal/mol) than
the 7a f 7c isomerization (8.5 kcal/mol) followed by the six-
(35) A similar feature was found in the reaction between dihydrido- membered σ-bond metathesis of 7c (8.2 kcal/mol). From these
(quinoline-8-acyliminol)bis(triphenylphosphine)iridium(III) and H2, in which
the ligand-assisted H-H splitting and the ligand-assisted H-H coupling results, it is clearly concluded that we can neglect the reaction
reversibly occur. course involving the 7a f 7d isomerization followed by σ-bond
3874 J. Am. Chem. Soc., Vol. 122, No. 16, 2000 Musashi and Sakaki

Figure 6. Energy changes in the RuH2(PH3)4-catalyzed hydrogenation of CO2 into formic acid. In parentheses are the energy differences from the
sum of reactants (kcal/mol; DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation).

metathesis, and that formic acid is produced through the 7a f nates with Ru after PH3 dissociation to afford RuH(η1-OCOH)-
7c isomerization followed by the six-membered σ-bond me- (PH3)(H2) and the six-membered σ-bond metathesis of this
tathesis via TS7c-8c. complex takes place with a smaller Ea value than the five-
4.5. Energy Changes in the Ru-Catalyzed Hydrogenation membered H-OCOH reductive elimination. As a result, the
of CO2 into Formic Acid. We have completed all the reaction proceeds through 1a f 2a f TS2a-3a f 3a f 3b f
preparations to discuss energy changes along the RuH2(PH3)4- 7a f TS7a-7c f 7c f TS7c-8c f 8c f 1b + HCOOH, in
catalyzed hydrogenation of CO2 into formic acid.36 Above which the rate-determining step is also the CO2 insertion (Ea )
results indicate that (1) the six-membered σ-bond metathesis is 29.4 kcal/mol) and the second largest barrier is the PH3
the easiest reaction course to yield formic acid from the dissociation in 3a (19.1 kcal/mol). If PH3 dissociates from 1a,
ruthenium(II) formate complex, while the substitution of H2 for the catalytic reaction takes place through the CO2 insertion into
PH3 must occur to perform the σ-bond metathesis; and (2) if the Ru-H bond of cis-RuH2(PH3)3 followed by the six-
the substitution of H2 for PH3 cannot occur, not the σ-bond membered σ-bond metathesis; 1b f 2b f TS2b-3b f 3b f
metathesis but the five-membered H-OCOH reductive elimina- 7a f TS7a-7c f 7c f TS7c-8c f 8c, in which the rate-
tion must take place as the last step. On the basis of these results, determining step is the CO2 insertion (Ea ) 10.3 kcal/mol). From
the following conclusions are presented about the reaction these results, it should be clearly concluded that if phosphine
course: If PH3 does not dissociate from Ru, the reaction dissociates from Ru, this catalytic reaction easily proceeds.
proceeds through the CO2 insertion into the Ru-H bond of cis- Actually, Jessop et al. experimentally reported that the addition
RuH2(PH3)4 followed by the five-membered H-OCOH reduc- of excess phosphine suppressed the reaction.10 Thus, the use of
tive elimination from RuH(η1-OCOH)(PH3)4; i.e., 1a f 2a f solvent that facilitates phosphine dissociation is recommended.
TS2a-3a f 3a f TS3a-4a f 4a f TS4a-5a f 5a f 6a f 1a Also, the ruthenium(II) complex that has three phosphine ligands
+ HCOOH, in which the rate-determining step is the CO2 is expected to be a good catalyst.
insertion (Ea ) 29.3 kcal/mol), as shown in Figure 6. However, 4.6. Electronic Process of the CO2 Insertion into the Ru-
if PH3 can dissociate from 3a, the reaction mechanism changes. (II)-H Bond. As described above, the CO2 insertion into the
In this case, not the H-OCOH reductive elimination but the Ru-H bond is the rate-determining step. Also, the six-
six-membered σ-bond metathesis takes place, since H2 coordi- membered σ-bond metathesis is of considerable importance,
since the reaction course would be changed if this σ-bond
(36) We estimated the activation energies of several important steps with
the MP4(SDQ) method to examine if the DFT(B3LYP) method yields
metathesis was neglected. Thus, it is worthwhile to investigate
reliably the activation barrier. When the DFT(B3LYP) and MP4(SDQ) electronic processes of these reactions. As shown in Figure 7,
methods yielded considerably different values, we further calculated it with C atomic population considerably increases and O1 and O2
the CCSD(T) method. In the CO2 insertion step (2b f TS2b-3b), the Ea atomic populations moderately increase in both insertion reac-
value was calculated to be 10.3, 14.2, and 11.0 kcal/mol with DFT(B3LYP),
MP4(SDQ), and CCSD(T) methods, respectively, showing that the DFT- tions of 2a and 2b, while Ru atomic population significantly
(B3LYP) value is similar to the CCSD(T) value. In the five-membered decreases in both, where natural bond orbital population was
reductive elimination (4b f TS4b-5b), the Ea value was calculated to be adopted.37 However, H2 atomic population little changes. These
17.5 kcal/mol with the DFT(B3LYP) method and 16.0 kcal/mol with the
MP4(SDQ) method. In the isomerization of 7a to 7c, the Ea value was features suggest that the charge transfer to CO2 from H2 occurs
calculated to be 8.5 kcal/mol with the DFT(B3LYP) method and 9.5 kcal/ considerably, and at the same time, H2 is provided electrons
mol with the MP4(SDQ) method. In the six-membered σ-bond metathesis from Ru, as shown in Scheme 2. The other important feature
(7c f TS7c-8c), the Ea value was calculated to be 8.2 kcal/mol with the observed in Figure 7 is that the populations little change upon
DFT(B3LYP) method and 9.3 kcal/mol with the MP4(SDQ) and CCSD(T)
methods. These results suggest that the DFT(B3LYP) method, as well as (37) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. ReV. 1988, 88,
MP4(SDQ) and CCSD(T) methods, provides a reliable activation barrier. 899.
Ru-Catalyzed Hydrogenation of CO2 into HCO2H J. Am. Chem. Soc., Vol. 122, No. 16, 2000 3875

responsible for the larger Ea value of the insertion reaction of

2a. Their contour maps are shown in Figure 8. In TS2a-3a, the
HOMO involves considerable antibonding overlaps between Ru
d and O p orbitals and between Ru d and H 1s orbitals. On the
other hand, the HOMO of TS2b-3b involves the antibonding
overlap between Ru d and O p orbitals and nonbonding
interaction between Ru d and H 1s orbitals. As a result, the
HOMO of TS2a-3a is much less stable than that of TS2b-3b.
The next question is why the antibonding interaction between
Ru d and H 1s orbitals is involved in TS2a-3a but not in TS2b-3b.
This would be interpreted in terms that the H2 ligand is forced
to take the position that suffers from the antibonding interaction
with the Ru d orbital because of the congested structure of
TS2a-3a. In TS2b-3b, CO2 can take a better position, due to the
less congested structure, and therefore, the reaction system can
avoid the unfavorable situation in which H2 gives rise to an
antibonding overlap between Ru d and H 1s orbitals. The
difference in behavior of molecular orbitals at lower energy is
also understood in terms of the Ru-O1 bonding interaction, as
follows: φ50 and φ51 of TS2a-3a involve weaker Ru-O1 bonding
than φ41 and φ42 of TS2b-3b, due to the longer Ru-O1 distance
in TS2a-3a than that in TS2b-3b. The long Ru-O1 distance in
TS2a-3a also arises from the congested structure.
4.7. Electronic Process of the σ-Bond Metathesis. In both
six-membered and four-membered σ-bond metatheses, Hβ
atomic population significantly decreases, while HR atomic
population moderately increases, as shown in Figure 9. These
population changes clearly show that both σ-bond metatheses
occur through heterolytic bond cleavage of H-H. This feature
is essentially the same as that of the ligand-assisted H2 splitting
in Ir(III) and Pd(II) complexes previously reported.13-15
Figure 7. Population changes in the CO2 insertion into the Ru-H Significant differences are observed between four-membered
bond of RuH2(PH3)n (n ) 3 and 4): Natural bond orbital population37 and six-membered σ-bond metatheses: the Ru atomic population
with DFT(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation. A positive gradually increases in the six-membered σ-bond metathesis,
value represents an increase in the population relative to the precursor while it little increases at the TS but suddenly increases at the
complex. product in the four-membered σ-bond metathesis. Also, the O1
atomic population increases at the TS and then decreases at the
Scheme 2
product in the four-membered σ-bond metathesis, while it little
changes in the six-membered σ-bond metathesis. These features
suggest that electron distribution smoothly changes in the six-
membered σ-bond metathesis but it does not in the four-
membered metathesis. This difference is interpreted in terms
of orbital interaction, as follows: In the four-membered σ-bond
metathesis, the O1 lone pair orbital of formate must change its
going to the product from the TS. This result clearly indicates direction toward Hβ to form the O-H bond, as shown in Scheme
that formate is almost formed at the TS, as displayed by 3. This direction change weakens the CT interaction with Ru
geometry changes. and decreases the Ru atomic population. Approach of formate
It is noted that O1 atomic population increases at the TS but to H2 induces the polarization of the H2 moiety so that the HR
then decreases at the product in the insertion reaction of 2a, atom becomes more negatively charged and the Hβ atom
while it little decreases at the product in the insertion reaction becomes more positively charged. This polarization enhances
of 2b. This difference suggests that the charge transfer from the charge transfer from HR to Ru. Thus, the Ru atomic
O1 to Ru is difficult at TS2a-3a in the insertion reaction of 2a, population little changes at the TS, due to the compensation of
probably because the O1 atom cannot easily approach Ru due these two CT interactions. At the product, the HR ligand
to the congested geometry of TS2a-3a (see the geometry changes completely becomes hydride. Since the hydride ligand substan-
shown in Figure 1). tially donates electrons to Ru, the Ru atomic population
The orbital energy changes are compared between two considerably increases at the product. In the six-membered
insertion reactions, as shown in Figure 8. An important σ-bond metathesis, the situation is different; since the O2 atom
difference is that the HOMO becomes less stable upon going has a lone pair orbital which expands toward the Hβ atom in
from 2a to TS2a-3a but becomes more stable upon going from 7c, the O2-Hβ bond can be smoothly formed without consider-
2b to TS2b-3b. The next notable difference is that φ50 and φ51 able weakening of the Ru-O1 bond in the six-membered σ-bond
significantly rise in energy upon going from 2a to TS2a-3a, while metathesis. Because of these smooth bond formations, the
φ41 and φ42 moderately rise in energy upon going from 2b to electron distribution smoothly changes in this σ-bond metathesis.
TS2b-3b (note that φ50 and φ51 of TS2a-3a correspond to φ41 The above discussion suggests that the O-H bond is more easily
and φ42 of TS2b-3b, respectively). These differences are formed in the six-membered σ-bond metathesis than in the four-
3876 J. Am. Chem. Soc., Vol. 122, No. 16, 2000 Musashi and Sakaki

Figure 8. Energy levels and contour maps of several important molecular orbitals in the CO2 insertion in cis-RuH2(PH3)n (n ) 3 and 4): DFT-
(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation. Contour values are from -0.525 e‚au-3 to 0.525 e‚au-3 at intervals of 0.025 e‚au-3. Solid lines
represent positive and zero contours, and dotted lines represent negative contours.

membered σ-bond metathesis. Actually, the formate moiety is moderate Ea value (8.2 kcal/mol); and (4) the phosphine
more stable in TS7c-8c than in TS7a-8a by ca 10 kcal/mol, where dissociation in cis-RuH2(PH3)4 and cis-RuH(η1-OCOH)(PH3)4
the calculation was carried out for the formate anion whose is necessary for the σ-bond metathesis.
geometry was taken to be the same as that in TS7a-8a or TS7c-8c. From the above results, we can conclude that the reaction
This energy difference roughly corresponds to the difference mechanism depends on the reaction conditions; when PH3
in Ea between six-membered and four-membered σ-bond cannot dissociate from Ru, the precursor complex for the σ-bond
metatheses. From these results, it is concluded that the six- metathesis cannot be formed and only the H-OCOH reductive
membered σ-bond metathesis more easily takes place than the elimination can take place. Thus, the hydrogenation of CO2 into
four-membered one because the O-H bond is more easily formic acid takes place through the CO2 insertion into the Ru-H
formed in the former than in the latter. bond of cis-RuH2(PH3)4 followed by the H-OCOH reductive
elimination, where the rate-determining step is the CO2 insertion
5. Conclusions (Ea ) 29.3 kcal/mol). When PH3 can dissociate from Ru in cis-
All of the possible elementary steps involved in ruthenium- RuH2(PH3)4, CO2 is much more easily inserted into the Ru-H
catalyzed hydrogenation of CO2 into formic acid were theoreti- bond with a much smaller Ea value (10.3 kcal/mol), and the
cally investigated with the DFT(B3LYP) method. Since cis- resultant complex, cis-RuH(η1-OCOH)(PH3)3, easily undergoes
RuH2(PMe3)4 was experimentally used as a catalyst, we adopted the six-membered σ-bond metathesis with H2, where the rate-
cis-RuH2(PH3)4 as a catalyst model. Important results are determining step is the CO2 insertion. Apparently, the PH3
summarized, as follows: (1) the CO2 insertion into the Ru-H dissociation facilitates this catalytic reaction. Actually, it was
bond occurs with difficulty in cis-RuH2(PH3)4 but occurs easily experimentally reported that addition of excess PMe3 suppressed
in cis-RuH2(PH3)3; (2) the H-OCOH reductive elimination the reaction.10c
requires a very large Ea value (40.3 and 44.8 kcal/mol for n ) From the above results, the use of solvent that facilitates
3 and 4, respectively) for the three-membered transition state phosphine dissociation is recommended in this catalytic reaction.
but a moderately large Ea value (25.5 and 17.5 kcal/mol for n Also, the Ru(II) complex that has three phosphine ligands is
) 3 and 4, respectively) for the five-membered transition state; expected to be a good catalyst.
(3) though the four-membered σ-bond metathesis of cis-RuH- It should be noted that the six-membered σ-bond metathesis
(η1-OCOH)(PH3)3(H2) requires a very large Ea value (24.8 kcal/ is the easiest reaction course to produce formic acid. If this
mol), the six-membered σ-bond metathesis occurs with a σ-bond metathesis was neglected, the five-membered reductive
Ru-Catalyzed Hydrogenation of CO2 into HCO2H J. Am. Chem. Soc., Vol. 122, No. 16, 2000 3877

Scheme 3

σ-bond metathesis into consideration when discussing the

reaction mechanism of transition metal catalyzed hydrogenation
of CO2 into formic acid; for instance, the six-membered σ-bond
metatheses of Rh(η1-OCOH)(PH3)2 and [RhH(η1-OCOH)-
(PH3)3]+ occur with nearly no barrier.38 The detailed investiga-
tion is in progress now.

Acknowledgment. All of the calculations were carried out

with HP Exemplar Technical Server V2250KS of Information
Processing Center of Kumamoto University and NEC-HPC of
Institute for Molecular Science (Okazaki, Japan). This work was
financially supported in part by the Grant-in-Aid for Scientific
Research on Priority Areas (the Chemistry of Inter-Element of
Linkage and the Molecular Physical Chemistry) from Ministry
of Education, Culture, Sports and Science (284 and 403).

Supporting Information Available: Figures of the DFT-

(B3LYP)-optimized geometries and energy changes in the
oxidative addition of H2 to Ru(PH3)n (n ) 3 and 4), figures of
the eigenvectors with imaginary frequency (DFT(B3LYP)/BS-
I) in the transition states of the CO2 insertion into the Ru-H
Figure 9. Population changes in the σ-bond metathesis of RuH(η1-
bond of cis-RuH2(PH3)n (n ) 3 and 4), the reductive elimination
OCOH)(PH3)3 with H2: Natural bond orbital population37 with DFT- of formic acid from RuH(η1-OCOH)(PH3)n (n ) 3 and 4), the
(B3LYP)/BS-II//DFT(B3LYP)/BS-I calculation. A positive value rep- σ-bond metathesis of RuH(η1-OCOH)(PH3)3 with H2, and the
resents an increase in the population relative to the H2 complex. isomerizations of 3a f 4a, 3b f 4b, 7a f 7b, 7a f 7c, 7a f
7d, and 7d f 7e. Energy levels of several important molecular
elimination of H-OCOH became the easiest reaction to yield orbitals for 2a, 2b, 7a, 7c, TS2a-3a, TS2b-3b, TS7a-8a, and
formic acid, since the five-membered reductive elimination TS7c-8c and their contour maps (PDF). This material is available
needs a smaller Ea value (17.5 kcal/mol) than does the four- free of charge via the Internet at http://pubs.acs.org.
membered σ-bond metathesis (Ea ) 24.8 kcal/mol). Thus, the
JA9938027
neglect of the six-membered σ-bond metathesis leads to a
different conclusion of the reaction mechanism, as follows: the (38) This six-membered σ-bond metathesis was not investigated in the
CO2 hydrogenation occurs through the CO2 insertion into the theoretical work of Rh(I)-catalyzed hydrogenation of CO2 into formic acid.12
We investigated the six-membered σ-bond metatheses of Rh(η1-OCOH)-
Ru-H bond followed by the five-membered H-OCOH reduc- (PH3)2 and [RhH(η1-OCOH)(PH3)3]+ with H2 and found that these reactions
tive elimination. This clearly shows the importance of the six- much more easily occurred with nearly no barrier than the four-membered
membered σ-bond metathesis. The six-membered σ-bond me- σ-bond metathesis. These results suggest that Rh(I)-catalyzed hydrogenation
tathesis is essentially the same as the formate-assisted H2 of CO2 into formic acid occurs with nearly no barrier and the six-membered
bond metathesis of the formate complex should be taken into consideration
activation which was previously proposed by Darensbourg et when discussing the reaction mechanism of rhodium(I)- and rhodium(III)-
al.7 As discussed above, we should take the six-membered catalyzed hydrogenations of CO2 into formic acid.