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REVIEWS

Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid


and Its Derivatives from C 0 2
Walter Leit ner*
Dediccrted to Profissor Henri Brunner on the occasion qf his 60th hirthcluy

The use ofcarbon dioxide as a raw mate- tion mechanisms must be found. The can to a large extent be attributed to the
rial for chcmical syntheses is an ecologi- catalytic reduction of CO, to formic fruitful interaction between investiga-
cally and economically valuable exten- acid and its derivatives has been inten- tive work into reaction mechanisms and
sion to the carbon sources used at the sively studied in recent years. A number the development of new catalytic sys-
present time. In order to convert the of new approaches to the synthesis of tems.
thermodynainically stable and compar- formic acid from CO, have reached such
atively unreactive CO, molecule into the a state of knowledge that continuing de- Keywords: CO, activation . formic acid
desired product in an efficient manner, velopment may well lead to industrial- * homogeneous catalysis . reductions .
suitable reaction conditions and activa- scale operation in the near future. This transition metal complexes

Tlirn \ i h u i uin he done on the Day qf Judgement, when k~inirrn sources are limited has led to a growth of scientific efforts to find
clcwl.c (irc ~iv~i~glied,with tliree t~sscryson.forniic acid, or with tliirtj,? alternative carbon sources since the early 1970s. Carbon dioxide
On ilw oilier kmd, what do we know oftlie Day of Judgemen1 has always attracted the greatest interest,[*.3 1 as Nature uses this
~ not kr?oit everything tliut might come out oflfbrmic acid
i f ' i ido
compound so successfully as a synthetic building block in pho-
h,v lhui tiiw'' tosynthesis-the basis of life on earth.
Robert M u d , The M a n without Qualities
The carbon reserves on our planet in the form of CO, and
CO: - are for practical purposes inexhaustible, exceeding the
1. Carbon Dioxide as a Raw Material carbon content of the deposits of fossil raw materials many
times over. Since the beginning of industrialization in the second
1.1. CO, as an Environmentally Friendly C, Building half of the last century, mankind has "produced" CO, in in-
Block creasing amounts and released it into the atmosphere. The most
important source of anthropogenic CO, emission is the combus-
The number of different chemical compounds produced tion of fossil fuels for energy production. The destruction of
worldwide at the present time is roughly in the range 20000- biomasses also contributes indirectly to the increase in the con-
30000."] This large number of substances is produced from centration of atmospheric CO,. In 1989. the total amount of
only ;i very few basic chemical raw materials, the source of CO, added to the atmosphere due to human activity was ap-
carbon being almost exclusively fossilized matter. namely min- proximately 7 x lo9 t carbon. The possible connections between
eral oil. natural gas, and coal (Fig. 1). The fact that these re- anthropogenic CO, emission, the increasing C 0 2 content of the
atmosphere, and the global climate
have for some years been exhaustively
Fossil raw materials
intermediates
F l investigatedl4] and discussed.[*" 5. 61

'
I Estimating the risks that would fol-
plastics. pharmaceuticals.
mineral or1 natural gas coal CO. methanol. arenes. plant proteclcon agents.
ethylene oxide. acrylic acid elc ferllllzels. etc low from a global climatic change and
developing strategies for the preven-
I31 [300) I,,,( tion of further increase in the atmo-
Fig. I , I hc ran material basis of the cheinlcal industry spheric C 0 2 concentration are un-
doubtedly important tasks. In this context, the use of CO, as a
[*] Priv.-L)or. Dr. W. Leitner raw material for chemical synthesis can only make a very small
M;ih-PlnncL~lii\titut l'ur Kohlenlorschunp contribution. Realistically. only a responsible use of primary
1. D-45470 Mulhcim an der R u h r (Germany)
K;ii~c~-Willicliii~PIat;.
TclcI;t.r +
In[. code (208)306-2980 energy and a greater utilization of nonfossil and ideally renew-
c-mill leifncr,<linpi-iiiiielhc1m.mpg.d400.de able energy carriers will ever be able to achieve a major reduc-
REVIEWS W. Leitner

tion in the release of CO,. At the same time, this also means that From the safety aspect, carbon dioxide is an ideal raw mate-
enough “waste CO,” will be produced to provide a carbon rial, as can be seen from a comparison of its properties with
source sufficient for a multitude of chemical requirements. even those of the widely used C , starting compounds carbon monox-
allowing for large reductions in anthropogenic carbon dioxide ide (CO) and phosgene (COCI,) (Table 1). For example, CO, is
emissions. For example, a typical coal-fired power station with practically nontoxic, and can be stored, transported, and han-
desulfurization of the exhaust gas produces 830 kg CO, per dled without problems.
MWh electric power, and a power station fired with natural gas
produces 400 kg CO, per MWh. In the exhaust gases from coal-
fired power stations, the CO, concentration can reach 14%.[61 1.2. Why Formic Acid?
In principle, an “anthropogenic CO, cycle” could therefore
be achieved without making additional demands on the natural Most current applications of carbon dioxide are based on its
reservoir of carbon. However, most of the CO, bought and sold physical or physico-chemical properties.[’, 91 However, CO, is
on the world market does not come from this over-abundance, already being used as a raw material in some industrially impor-
but from hydrogen production [Eqs. (a) and (b)].“I It is possible tant chemical reactions.[2h1For example, the direct hydrogena-
tion of CO, plays an important role in the industrial synthesis
of methanol from H,,CO/CO, mixtures (ICI process).[”’ In
principle, the reduction of CO, also provides a potential ap-
proach to a number of other important products as shown in
in principle to extract CO, from power station exhaust gases by Scheme 1. The reduction equivalents required for the individual
the same methods that have been developed for extracting it transformations can be made available by addition of hydrogen
from process gases of hydrogen production.[2g.61 The method as shown in Scheme 1 or by electron transfer processes. The
that is growing most rapidly in importance in this context is
absorption in aqueous solutions of amines. The trend towards
recovery of CO, will probably greatly intensify in the future,
leading to the increasing availability of large quantities of this
cheap raw material.

Table 1. Properties of various C , building blocks [a]

co,

+4H2 3 +*HZ
CO COCI,

MAK value
toxicology
30 ppm
iiffinity for hemo-
globin 210 times
0.1 ppm
war gas
SO00 ppm
danger 01‘
asphyxiation a t
(z ) 4
* -2H20 -H20
[F)
I
that of O2 10 V O I ~ ! in
~ air
LC,,, (inhal. mouse) 2444 ppm (4 h) 110 ppm (30 min)
environmental ycs high “negativc“
hazard
flammability 12 74 vol “A
~ no no
boiling point -192 c XC -78 C (subl.)
storage only at pressure very difficult. to be no problem
5 3 . 5 MPa aboided + H2
transport gas bottles or only possible (or gas bottles or
tanks kilogram quantities tanks
solubility in 1 mL 0.17 mL miscible in all 3.45 mL
toluene at 20 C proportions

[a] Data taken from ref? [8 101


~ Scheme 1. Reduction of CO, ;is ii source for industrially important products.

f Walter Leitner was born in 1963. studied chemistry in Regensburg, bvhere he obtained his
Doctorate under Prof. H . Brunner in 1989. After a period of post-doctorate research with
John M . B r o w at the Dyson Perrins Laboratory at ihe Universiry of O.xufi)rdhe relurned to
Regensburg in 1991 us u Liebig Fellow, and began his reseurch into the catalytic hydrogenation
of‘ carbon dio.uide. In 1992, ht’ moved to the research unit “CO, chemistry” of the Max-Planck-
Gesellschaft led by Prof: E. Dinjus at the University of Jena, where he habilitated in the
Inorganic Cheniistrj. Department. Since June 1995, hc has been uc,tive ut the Mu.u-Phck-ln-
stitut ,fur Kohlenfbrschr~ngin Miilheini an der Ruhi.. His speciul,fXd of research is the use of
transition nietal compounds in homogeneous cztalj..yis und the understanding of their mode of
action.
CO, a5 a Ra\4 Material REVIEWS
very first product of the reduction of CO, in this scheme is 2. Reduction of CO, by Electron Transfer
formic acid.
Approximately 300000 t formic acid is produced annually 2.1. Electrochemical Reduction of CO, to Formate
worldwide.["I most of which is consumed in silage for animal
feeds. Large amounts are also used in the leather and textile The one-electron reduction of COz to the radical anion C 0 ; -
industries for tanning and dyeing. Formic acid is also employed [Eq. (f)] requires a reduction potential of - 1 .Y V.[''] The high
as a coagulating agent in the production of latex rubber, and it energy species C0;- reacts readily with H' sources to give the
is sometimes used as a food preservative (E236j. The reducing formate ion, but other possible reaction routes such as dispro-
properties of formic acid are often exploited in preparative syn- portionation. dimerization with formation of oxalate, or further
thetic chemistry. (Leuckart- Wallach reaction, Eschweiler- reduction are difficult to suppress.
Clark methylation, transfer hydrogenolysis,[' 3 1 and transfer hy-
drogenation["]). Nitro compounds can be reduced to amines
batchwise in large-scale processes by catalyzed reduction with
formic acid or ammonium formate. Many derivatives of formic An alternative and very promising approach to the electro-
acid. such as sodium formate (a component of de-icing salts and chemical reduction of CO, involves the production of a suitable
photographic fixing baths), methyl formate (DMF production), catalyst at the electrode to enable formate or formic acid to be
ethyl formate (flavoring), and dimethyl formamide (solvent) are formed directly from CO,, H+ions, and twoelectrons [Eq. (gj].
also of considerable economic importance.
Since the two-electron reduction to formic acid requires a con-
Formic acid was isolated in the pure state for the first time in
siderably lower potential than the one-electron reduction, the
1749 by Markgraf by dry distillation of red ants. On an industri-
electrolyses in the presence of catalysts can be carried out at
al scale. formic acid was for many years produced exclusively by
considerably lower voltages. However, it is still a problem to
the reaction of CO with hot sodium hydroxide solution at high
control the selectivity between the various two-electron reduc-
pressure and subsequent acidification with dilute sulfuric
acid. Large quantities of the unwanted by-product sodium sul- tions [Eqs. (8)-(i)]. A general discussion of electrocatalytic CO,
Fdte are formed in this process. Considerable quantities of reduction can be found in reports and reviews of the original
formic acid are obtained as the by-product of the oxidation of research."', ''I
low boiling mineral oil fractions during the synthesis of COz + 2H' + 2e- ~-~+ HCO,H E' = - 0.61 V (g)
acetic acid.
At present. the most widely used method of producing formic COz + 2 H ' + 2e- ~~ t CO + H 2 0 E = - 0.53 \ (h)
acid is based on the two-stage process of Equation (c).["] In the
2Hi +2e- -+ H, ,f? = - 0.41 \' (i)

Characteristic parameters of the electrocatalytic systems used


to produce formates by this principle include the overvoltage
required for the electrolysis, the current yield, and the number
of catalytic cycles (turnover number (TON)) for the formate
first stage. methyl formate is formed by the carbonylation of formation. For many years, the use of transition metal complex-
methanol, and this is then hydrolyzed to formic acid and es as electrocatalysts has attracted much attention, and typical
methanol in the second stage. The methanol is recovered and systems that form significant amounts of formate are listed in
returned to the first stage. The net process is therefore the addi- Table 2. In addition to the catalysts used in homogeneous phase
tion of water to CO. This reaction can also be carried out direct- or bonded in polymeric matrices. the use of metal complexes
ly under comparatively severe conditions in the presence of cer- adsorbed directly onto an electrode surface to produce formate
tain amines." '1 and formic acid has also been described.['*.2')1
The synthesis of formic acid by the reduction of CO, is an
With a number of catalysts. reaction conditions have a re-
interesting alternative to these processes; the energy balance of
markable influence on product distribution of the two-electron
the addition of H,O to CO and the reduction of CO, with H,
reductions (g)-(i). In the case of the complex [Ru(bpy),-
are very similar [Eqs. (d) and (e)].['O1The synthesis of formic
(C0),l2+,CO and H, are formed almost exclusively in the ratio
1 : 1 in H,O/DMF at pH 6.0, whereas, at pH 9.5 and under oth-
erwise identical conditions, all three possible products are formed
in the molar ratio CO/H,/HCO; = 2:3:3.[321I n acetonitrile. the
same catalyst causes formate to be produced in 44 catalytic cycles
with a current yield of more than 80% (Table 2. entry 3).lz3I and
the formation of D M F by the electrocatalytic reduction of CO,
in the presence of Me,NH has also been On the
acid from COz offers the possibility of using carbon dioxide as other hand, the structure of the nitrogen Iigand has a relatively
a raw material to the extent of approximately lo5 tonnes carbon small influence on the product The highly se-
per year. The state of development of the various approaches to lective reduction of CO, with the mono(bipyridine)complex
the synthesis of formic acid and its derivatives from CO, is [Ru(bpy)(CO),CI,] results from the formation of a polymeric
discussed below, with a strong emphasis on systems in which film of [(Ru"(bpy)(CO),),] at the surface of the electrode.[33c1
transition metal complexes are used as catalysts in a homoge- Similar observations were made with complexes of the type
neous phase. [Re(Lj(CO),X] (L = derivatives of bpy, X = halide). They lead

2209
REVIEWS W. Leitner

Table 2. Trailsition metal complexes in a homogeneous phase or a polymer matrix for the electrocatalytic formation of formate from CO,.

[a] Maximum total number of mols formic acid or formate per mol complex in the given reaction time. [bl Current yield in parentheses where known. [c] bpg = hipyridine.
dppe = Ph,P(CH,),PPh,. bpm = 2.2'-bipyriniidine. terpy = 2,2':6.?"-terpyridine. [d] N o information.

mainly to CO production by electrocatalytic reduction of C 0 2 plex cation [ R ~ ( b p y ) , ] ~ + . [ ' ~ .I~n ~the


- ~ preliminary
'] experi-
in organic solvents both in the homogeneous phase[17a.341 and ments, [Ru(bpy),12 was used with methylviologen, which was
+

in polymer films.[351They cannot be used for CO, reduction in intended to perform the electron transfer.[451However, it was
aqueous solution as hydrogen is liberated preferentially. How- found that the electron transfer was brought about by
ever, production of formate can successfully compete with the [Ru(bpy),] species produced by photolabilization of the bpy
formation of H, in water, if the complexes are incorporated in ligands from [ R ~ ( b p y ) , ] ~ + . [ ~Then,
~ " . ~over
' ~ ~a period of time,
a polymer matrix of Nafion and fixed to the electrode.[281 several systems for the photoreduction of CO, to formate
were developed based on the combination [Ru(bpy),]'+/
[Ru(bpy),(CO)(L)]"+ (L = CO, n = 2; L = H*Cl,n = l).[46,471
2.2. Photochemical Reduction of CO, to Formate
Triethanolamine in D M F is usually used as the reducing agent,
The fundamental principles of the photochemical reduction and quantum yields of up to 15% are obtained. Irradiation of
of CO, to formate are largely identical to those described in these systems with visible light (>.>320 nm) produces up to
Section 2.1. The one-electron reduction to C0,- requires ex- 3700 mol formate per mol catalyst within 20 h.[47b1The forma-
tremely strong reducing agents that are difficult to produce by tion of small amounts of formate has also been reported for the
photochemical means.[361Kubiak et al. recently reported that combination of [Ru(bpy),]'+ with macrocyclic nickel complex-
irradiation even by diffuse daylight enables the trinuclear cluster and for photosensitizers based on vanadium complex-
[Ni,(p,-I),(dppm),] to reduce CO, to the radical anion CO;-.
whose presence was demonstrated inter alia by its subsequent
reaction to give f ~ r m a t e . ' However,~~~] the two-electron reduc-
tion [Eq. (g)] also represents the most energetically favorable 2.3. Mechanistic Aspects of the Catalytic Formation of
route from CO, to formate in photochemistry. An approach Formate by Electron Transfer
closely related to electrocatalysis consists of using a photoactive
system to convert light into electrical energy, which is then used As shown schematically in Figure 2, the electrocatalytic and
with the help of a catalyst to reduce CO, .[16, photocatalytic reductions of CO, to formate differ only in the
Semiconductor materials in the form of electrodes, colloids, method of producing the electrons required for the reduction.
or powders are able to reduce CO, to formate as the principal The catalytic cycle leading to formate is the same in both cases,
product when photochemically irradiated, even without cata-
l y s t ~ .Systems
[ ~ ~ ~ reported to catalyze the formation of formate
in combinations with semiconductors include formate dehydro-
g e n a ~ e , [ ~m~e"t'h y l ~ i o l o g e n , [ metals,[39'
~'~~ ~ i1 and a ruthenium

complex.[401The formation of formic acid by photocatalytic


reduction of CO, in a supercritical phase has recently been

Organic photoactive systems also enable the direct[411and


c a t a l y ~ e d [ ~photochemical
~.~~] reduction of C 0 2 to formate to
be carried out in the presence of suitable reducing agents such as
triethylamine. However, ifp-terphenyl is used as the photosensi-
tizer with cobalt(r1r) complexes as catalysts, there is an increase
in the amount of CO produced relative to that of formate com-
pared to the catalyst-free system.[431
The most thoroughly investigated molecular photosensitizer Fig. 2. Principle of the electrocatalytic and photocatalytic reduction of CO, to
for the photochemical reduction of CO, to formate is the com- formate.

2210 Aiigw. Clienr. hi.G I E i i ~ ~1995.


l. 34. 2207 . 2221
C 0 2 ;IS a R ~ L Malerial
V REVIEWS

II I 7

////
A 6

3 + \cop
L
Schcnic 7 C':iI:~Iytic cycles in forinate formation by electron transfer with Ru"(bpy) catalysts [ R u ( b p ~ ) ~ ( C 0 ) ( L )(L
] " = CO. n = 2: L = H. n = 1 ) according
to rd;. [>It. 511. S i l v = solvent

and. in Fact. the same catalysts can often be employed. However. trocatalytic reduction of CO, can be explained by the protona-
a complex sequence of electron transfer steps and changes in tion equilibrium 5/6.[471Intermediates analogous to 5 and 6
the coordination sphere is necessary to build such a catalytic have also been suggested for the electrochemical reduction of
cycle1", ''I and the understanding of these combinations is a CO, to CO with [Re(L)(CO,)X] as catalysts, based on the re-
field of great current interest. sults of an in situ IR investigation.[34d1
The most extensively investigated catalysts for the electro- Two comparable cycles were recently shown to be responsible
chemical and photochemical reduction of CO, are of the type for the cobalt-catalyzed photochemical reduction of CO, with
[Ru(bpy),(C'O)(L)]"' (L = CO. n = 2; L = H, n = I ) , and the p-terphenyl as the photosensitizer.[431In this case, formate is
mechanisms for the electron transfer in formate formation illus- formed exclusively by a route analogous to A.[43'1 while the
trated in Scheme 2 have been elaborated in recent years regard- formation of a CO, adduct eventually leads to CO only.[43d1
less of the type of excitation. Both cycles include a common In addition to the difficulty of controlling the product selec-
catulyticull~active intermediate, namely the twice reduced sol- tivity, there is a further problem in the electrocatalytic and pho-
vent complex [Ruo(bpy),(CO)(Solv)] 1. tocatalytic reduction of CO, to formate. The concentration of
In Cycle A. the formate group is formed by the insertion of catalyst must be kept as low as possible to prevent deactivation
CO, into the Ru-H bond of the hydrido complex 31501in anal- processes. Even with the most active known catalysts. the con-
ogy to the hydrogenation of CO, (see Section 3.4). It was pos- centrations of reduction products in the reaction solution are
sible to detuct all the individual steps of this cycle, which leads therefore usually only in the millimolar range. In contrast, the
to the selective formation of formate, under catalytic conditions. methods of catalytic hydrogenation of C 0 2 to formic acid and
However. it was found in this study that an additional cycle was its derivatives described in the following Section, can lead to
responsible for thc reduction of CO, to CO cznd formate. This product concentrations of up to several mol per liter.
becomes thc dominant reaction route with [Os(bpy),-
(CO)H] ' . L r 4 1
This sccond route presumably involves Cycle B in which for- 3. Transition Metal Catalyzed Formation of Formic
mate is liberated from a metal carboxylic acid formed by proto- Acid and Its Derivatives from CO, and H,
nation of the r?'-CO, complex 5. Complex 5 was recently synthe-
sized by an independent route and characterized by X-ray 3.1. General Considerations
structural analysis.["1 The formation of 5 under the conditions
of electrocatalysis was detected spectroscopically. The pH-de- In the early 1970s, the pioneering work of several research
pendcnt simultaneous formation of HCO; and CO in the elec- groups showed that formic acid, its salts, esters. or amides are

221 1
REVIEWS W Leitner

accessible from hydrogen, carbon dioxide, and a possible third rhodium was obtained with Wilkinson's catalyst [Rh(PPh,),CI]
component in the presence of homogeneous transition metal under the conditions detailed in Table 3 (entry 2). At the end of
catalysts [Eqs. (j)-(m)]. the reaction, there is approximately a SO-fold excess of amine

-, - HCOzH ti)
relative to the concentration of the newly formed formic acid.
The presence of small amounts of water favors the hydrogena-
tion of COz. Later modifications to the process described in a
series of patents gave only small improvements to the original
s y ~ t e m . [ ~ The
~ " -highest
~~ TON (314) was reported with [Rh(P-

b-HC(0)OR + H,O- Ph,),CI] in a mixture of isopropyl alcohol, water, and NEt,


Very recently a complex with nitrogen ligands has been reported
to act as an effective catalyst for CO, hydrogenation in alcoholic
Since the synthesis of formic acid derivatives, unlike the for- solution.[54f1Up to 5000 turnovers are observed with the com-
mation of HC0,H or HCO;, requires not only the formation of plex cis-[Ru(6,6'-C12bpy),(H,0)z](CF,S0,), in EtOH/NEt, . In
the C-H bond but also the breaking and reforming of another the absence of aniine, the drastic reaction conditions (60 atm,
covalent bond during the reaction. these processes will be dealt 150 "C) lead to formation of ethyl formate (see Section 3.3.3).
with separately. In 1992, Nicholas and Tsai discovered that the hydrogenation
of CO, could also be carried out in the absence of bases.[551
However, with the catalyst [Rh(PMe2Ph),(nbd)]BF4 (nbd =
3.2. Synthesis of Formic Acid and Formates from CO,
norbornadiene) in T H F under similar high pressures, only
and H,
64 mol HCO,H per mol catalyst per day are formed. Again, the
presence of small amounts of water increases the activity of the
Table 3 summarizes typical catalytic systems used for the hy-
catalyst (Table 3, entry 6 ) .
drogenation of CO, to formic acid and formates. The maximum
At about the same time, we were able for the first time to
total number of catalytic cycles per metal center (turnover num-
report a system for transition metal catalyzed hydrogenation of
ber (TON)). and, where available, the maximum rate at which
CO, to formic acid in which TONS greater than 1000 and TOFs
the catalytic cycles can take place a t the beginning of the reac-
of approximately 40 h - can be obtained under mild conditions
tion (turnover frequency (TOF)) are also given. Further ex-
(Scheme 3).f5h"1 The catalyst is produced in situ from the dimer-
amples can be found in the original research cited.

3.2.1. Hydiwgenation of CO, in Organic Solvents


The Catalytic Systenns
In 1974, a Polish research group reported that a homoge-
neous titanium(I1) catalyst produced from TiCI, and magnesium
in T H F promoted the catalytic formation of Mg(HC0,)2 by
treatment with H, and CO, alternately.[521Up to 15 equivalents
of CO, per equivalent Ti" could be fixed this way.
A little time later, Y. Inoue et al. reported the catalytic hydro-
dppb = Ph2P-pphp
genation of CO, with phosphane complexes of transition metals
of Groups 9 and A yield of 22 mol formic acid per mol Scheme 3. Hydrogenation of C 0 2 to formic acid according to ref. [56a]

Table 3. Catalytic systems for the synthesis of formic acid oi- formates by the hydrogenation of CO,. RT = room temperature.

Entry Catalyst Solvent Additive P(H>);P(CO,) T TON [a] I T O F [b] Ref.


[bar] ['C] [hl W'I
1 TiC1,;Mg THF Mg l!l RT 15 24 [521
2 [RU(PPh;);(H):I benzene NEt,. H,O 28/25 RT 87 20 - [53a]
3 [Pd(PPh,),CI,] benzene NEt,. H,O 50i50 RT 15 - - [53 b]
4 [Rh(PPh,),CU iPrOH NEt,. H,O 50:30 40 314 [54 el
5 cis-[ R u( 6.6'-Cl2bpy),( H ,0),](CF,3S0,), EtOH NEt.3 3W30 150 5000 8 154q
6 [Rh(PMc,Ph),(nbd)]BF4 [c] THF HZO 4K48 40 128 48 ca. 3 1551
7 [:Rh(cod)(~i-CI)),]!dppb [c] DMSO NEt, 20,'20 RT 1150 n
I_ 39 ~561
8 I(Rh(cod)(~-H)).Iidppb [cl DMSO NEt., 20:20 RT 2200 18 375 1571
9 [Rh(dcpb)(hfacac)][c] DMSO NEt, 20:20 25 3005 [d] 31 [d] 1335 [581
10 PdCI, HI0 KOH 106i40 240 340 3 1671
11 Pd/C H,O Na,CO, 1.7! [el RT 113 46 35 [681
12 [Rh(TPPTS),Cl] [c] H,O HNMe, 20m 25 3440 11 1365 [d] [711
13 IR~(PMe,)JH),I COX,,, NEt,. H 2 0 85;12(3 [f] 50 7200 1400 1731

[a] Turnover number is the maximum total number of mols formic acid or forinate per metal center in the givcn reaction time [b] From the maximum initial rates of reaction.
the TON and TOF are usually derived from different experiments. [c] nbd = norhornadicnc. cod = cyclooctadienc. dppb = Ph,P(CH,),PPh,, dcpb = Cy2P(CH,),PCy2.
hfacac = hexafluoroacetylacetonate, TPPTS = P(C,H,SO,Na),. [d] Unpublished results. [el 1 .0 mol L - I Na,CO, without added COi atmosphere. [f] At reaction tempera-
ture.

222 2 Aiiqw. Cliwi7. In!. E d Eiifil. 1995 34, 2207-2221


CO, as a Raw Material REVIEWS
ic rhodium complex [{(cod)Rh(p-Ci)],] 7 (cod = I ,5-cycloocta- possible catalytic cycles, but also by the rate at which these take
diene) and the bidentate phosphane Ph,P(CH,),PPh, (dppb). A place. Systematic studies of catalyst optimization have so far
mixture of DMSO and NEt, is used as the reaction medium. only been reported for the rhodium-catalyzed hydrogenation of
The final concentration of formic acid, under the conditions CO, to formic acid in DMSO/NEt,.[”. s 8 , 6 0 1

given in Scheme 3, is 2.1 mol L- and rweeris the concentration
of the amine by 65 %. In contrast to all other systems. water has
Catalyst Optimization in the. Rhoctium-Catu!v-e(/y=~~~~
Hydrogenation
a detrimental effect on the performance of this catalytic system.
ofCO, to Formic Acid
In the absence of amine, only small amounts of formic acid are
formed, similar to those observed in THELs7] Variation of the phosphane component has a considerable
effect on the activity of the catalyst formed with 7
of’ CO, Hydrogenation
Tiic Tlrrrmorl~~iirtnzic.s (Scheme 3).u6O1 When in situ catalysts are formed from 7 and
monodentate phosphane ligands PR, (Rh:P = 1 :4), the ob-
The drastic effect of the reaction medium on the maximum
served ligand effects can be explained by classical ligand con-
yield of formic acid can be explained by the thermodynamic
cepts such as basicity[6’,621 and steric demand[”’] of the PR,
balance^'"' i n the addition of H, to CO, [Eq. (n)]. Under stan-
groups. For PR, ligands of comparable size. the most active
catalysts are obtained with phosphanes of medium basicity
(pK,,(HPR:) z 4). The activity of such catalysts corresponds
approximately to that of the system 7/dppb. Both more strongly
acidic and more strongly basic phosphanes lead to rapid de-
dard conditions. this reaction is exothermic (approximately crease in the activity. With similar basicity, the activity decreases
- 32 kJ mol I ) , but strongly endoergic (+ 33 kJ mol- ’) be-
~ with increasing bulkiness of the ligands. and phosphanes PR,
cause of the unfavorable entropy conditions (two gases reacting with a cone greater than 180L are not suited as cocat-
to form a liquid with strong intermolecular hydrogen bonds). alysts for in situ systems 7/PR, in the hydrogenation of CO,.
To obtain high yields of formic acid, the entropy difference These rules cannot be applied to in situ catalysts with biden-
between the starting materials and the product must be reduced tate phosphanes, as with these ligands the size ofthe chelate ring
by a suitable choice of reaction conditions. formed on the metal center has a very important effect on the
Full reversibility of formic acid formation was demonstrated activity of the catalyst.[”. 631 However, even with constant chain
experimentally for the first time for the catalytic system shown length, the trends observed with monodentate phosphanes no
in Scheme 3. This enabled the effect of reaction conditions and longer apply, as can be seen from the increase in the activity of
the reaction medium on the yields and hence on the position of the in situ catalysts 7/R,P(CH2),PR, in the sequence
the equilibrium to be systematically investigated.[571As expect- R = Ph<Me<Cy<iPr.
ed for an exothermic reaction between two gaseous reactants, When the in situ catalyst 7/dppb is used. the catalytically
the equilibrium concentration increases as temperature decreas- active species is formed slowly compared with the rate of the
es and pressure increases. actual catalytic cycle, as proved by the marked induction period
The solvent is very important for the yield of formic acid, as on the first use of a catalyst solution.[s71This induction period
it can strongly influence the entropy difference by solvation of can be avoided by treating the catalyst solution with H, or
both the reactants and the product. The main reason for the HCO,H before reaction. However, even under these conditions,
special suitability of dipolar aprotic solvents for the hydrogena- only some of the rhodium complex appears to be converted into
tion of COz to formic acid was shown to be the solvation of the the catalytically active species, as indicated by the effect of acti-
product with cleavage of the hydrogen bonds. At the same time. vation on the turnover frequency. It is therefore impossible to
it is assumed that these solvents also affect the catalytic activity know to what extent the observed ligand effects are associated
by stabilizing intermediate stages of the catalytic cycle (see Sec- with the influence of the phosphanes on the course of the cata-
tion 3.4). lytic cycle or on the formation of the catalytically active interme-
As mentioned above, the addition of trialkylamine is not ab- diate.
solutely necessary for the catalytic hydrogenation of CO, under As explained in detail in Section 3.4, it is highly probable that
the conditions given in Scheme 3, although it too leads to cleav- electronically and coordinatively unsaturated molecules of
age of the hydrogen bonds and hence to a drastic increase in the [(P,)RhH] 11 (Scheme 4; P, = bidentate phosphane) represent
equilibrium concentration. With formic acid, trialkylamines d o the catalytically active intermediate in the rhodium-catalyzed
not form true 1 : l salts. but form liquid azeotropes with the hydrogenation of CO, in DMSO/NEt,. The aim of the develop-
composition HCO,H,”R, = 1.5-2: 1.[s91 The final concentra- ment of catalysts must therefore be to produce these species
tion of formic acid only exceeds the concentration of the amine under catalytic conditions in a rapid and well-defined reaction.
when such azeotropes can be formed and ratios of approxi- At the same time, a stable and easily produced precursor should
mately 1 : 1 arc observed with secondary amines.[”] In contrast be used and wide variation in the phosphane component is
to the reactions described in Section 3.3, the use of dimethyl- desirable.
amine as the amine component does not lead to further reaction To avoid the reduction stage in the formation of the catalyti-
of the formic acid to give dimethylformamide under the mild cally active intermediate 11, the hydrido complex [((cod)Rh(p-
conditions indicated in Scheme 3. H)),] 8 was tested as a precursor for in situ catalysts (Table 3,
The catalytic systems for the hydrogenation of CO, (Table 3) entry 8). which proved to be considerably more effective
are. of course. not only characterized by the total number of than systems formed with 7.[s71A lower limit for the maximum

221 3
REVIEWS W Leitner

Like allylrhodium complexes, acetylacetonatorhodium com-


plexes are able to form neutral monohydrides by hydrogenoly-
sis,["] and in fact the hexafluoroacetylacetonatorhodium com-
plexes of type 10 prove to be ideal catalyst precursors for the
hydrogenation of CO, to formic acid.[581The formation of
formic acid starts at maximum velocity without an induction
period, and the complex shows its full catalytic activity even at
concentrations of 5 x mol L- The turnover frequency of
10 565 h - ' obtained with complex 10 corresponds to the lower
9 /
limit of catalytic activity estimated for the in situ system 8jdppb.
Interestingly, in complexes of type 10, relationships are found
between the P-Rh-P angles in the solid state, the lo3Rh NMR
shifts in solution, and the catalytic activities in CO, hydrogena-
tion.['*] The cyclohexyl derivative [(Cy,P(CH,),PCy,)-
Rh(hfacac)] (Table 3, entry 9), with a maximum T O F of
1335 h - ' under mild conditions (40 bar, 2S"C), is the most
active catalyst so far reported for direct hydrogenation of CO,
11 to formic acid or formates in organic solvents. Under compara-
Scheme 4. Formation of the active intermediate 11 froni the various catalyat pre- tively mild conditions, similar high TOFs are obtained only in
cursors in the catalytic hydrogcnation of CO, to formic acid in DMSO:NEt,. aqueous solution. The complex [Ru(PMe,),(H),] enables a
P = PPh,: maxiinuni TOF: 7:dppb: 39 hK1 [jba]; 8;dppb: 370 h - ' 1571; 10:
565 h - ' [58]. T O F of 1400 h - ' to be obtained only at pressures exceeding
200 bar (Table 3. entry 13).

turnover frequency of the system Sjdppb has been estimated to 3.2.2. Hydrogenation of' CO, in Aqueous Solution
be 370 h - ' under the conditions indicated in Scheme 3, that is,
it was possible to increase the activity of the catalyst by a factor The hydrogenation of CO, to formic acid in aqueous solution
of 10 compared with that of the system 7/dppb (Scheme 4). is a particularly attractive approach to the utilization of carbon
As shown in recent research.[641and contrary to earlier opin- dioxide as a raw material, as water Is the usual solvent for the
ion,["] the catalytically active intermediate 11 is not formed recovery of CO, from process flue gases (Section 1.1). Thus,
directly from 8 and dppb (Scheme 4). Instead, the ti3-cy- aqueous solutions of amines could be used as both absorber and
clooctenyl complex 9 is formed by the reaction of 8 with dppb reaction solutions.
by hydride transfer. Complex 9 was identified unambiguously It has been known for some time that at temperatures above
by N M R spectroscopy and X-ray structural analysis (Fig. 3). 200 C in an atmosphere of CO, and hydrogen, potassium for-
Complex 9 is the actual catalyst precursor, reacting readily in mate is formed in aqueous potassium hydroxide solution, PdCI,
a hydrogen atmosphere to form the neutral monohydride being the catalyst (Table 3, entry The formation of sodi-
1 1 ,[64b.651 um formate from Na,CO, and hydrogen in aqueous solution in
the presence of a heterogeneous PdjC catalyst can also be re-
garded as an example of CO, hydrogenation (Table 3, entry
1 With K[Ru(EDTA-H)CI].H,O as a catalyst for the wa-
ter gas shift reaction in neutral aqeous solution, formic acid was
observed as a possible intermediate in a stoichiometric and
catalytic reaction.""]
Phosphane complexes of transition metals successfully used
as catalysts in organic solvents cannot be used in aqueous solu-
tion owing to their insolubility in water. Alcohol/water mixtures
have been used as reaction media for phosphane-containing
catalysts, although they have no particular advantages com-
pared with purely organic We have been able
to demonstrate that aqueous solutions of rhodium com-
plexes of the water-soluble phosphane (C,H,-m-SO;Na+),P-
(TPPTS)I7'] give homogeneous catalytic systems that can lead
to even higher activities and yields than obtained in organic
solvents (Scheme 5).["]
In situ catalysts can be employed for the hydrogenation of
'Li CO, in aqueous solution using TPPTS and the same rhodium
Fig. 3. Molecular structure of the t$cyclooctenyl complex 9 in thc solid state. precursors as in organic solvents. However, the most effective
Selected inlevatomic distances [A] and angles ["I. Rh-C(1J 2.2t9(10). RhbC(2) catalyst was found to be the water-soluble analogue of Wilkin-
2.122(10). Rh C(3)2.209(10). Rh-P(1) 2.237(3), Rh - P(2) 2 228(3), C(i)-Rh-C(3)
68.8(4). P( 1 )-Rh-P(2) 95.63(1O ) , C(2)-C(i)-C(3) 124.0( to), O(P(1)-Rh-P(Z)]![C( 1)- son's catalyst [(TPPTS),RhCI] 12, yielding up to 3440 mol
Rh-C(3J] 6. formic acid per mol catalyst (Table 3, entry 12).[71a1The hydro-

2214 Ai~gc'n.C'lwtn. In1 Ed. Eiigl. 1995. 34. 2201 -2221


C 0 2 215 ;I Raw Material REVIEWS
H20, Me2NH not seem to be stable under these possibly be-

H2 + COP . p" = 40 bar, T = RT, t = 12 h

[CIRh(TPPTS),], 12
HCOZH
cause of the formation of inactive carbonate species.["' 741
The presence of triethylamine and small amounts of water is
a necessary precondition for the production of formic acid by
the hydrogenation of C 0 2 in a supercritical phase.r731
After the
TON = 3440
equilibrium concentration has been reached, the HCO,H/NEt,
ratio is approximately 1.6: 1, just as when DMSO is used as the
solvent. In the presence of dimethylamine. HCOzH reacts fur-
ther to form DMF (see Section 3.3.2),1'5"1 whereas in the ab-
sence of an amine, no formic acid is formed at all. Other bases,
such as K,CO,, which are immiscible with the supercritical
Scheme 5. Hydrogenation of C 0 2 lo formic acid in aqueous solution according to phase, lead to TOFs of less than 10 h-'.
ref [71 :I[.

3.2.4. Isolation oJ' Foiwic Acid Produced by the Hydvogenation


or co,
genation of CO, begins without an induction period at maxi-
mum velocity, TOFs of up to 1365 h-' being reached.[71b1In Thus. a series of extremely effective catalytic systems for the
contrast to the reaction in organic solvents, the concentration of synthesis of formic acid from CO, and H, is now available.
the amine is never exceeded in aqueous systems, and no reaction High yields of formic acid in the homogeneous transition metal
occurs in the absence of amine.[""] Formation of the free for- catalyzed hydrogenation of CO, can be achieved if the equilibri-
mate anion was confirmed by 13CNMR spectroscopic measure- um of Equation (n) can be shifted by minimi7ing the entropy
ments on the reaction product, and in agreement with thermo- difference between the starting materials and the product in
dynamic considerations the formate anion was shown to be favor of formic acid. Independently of the reaction conditions,
stable towards decomposition even in the presence of an active the best method of achieving this seems to be the addition of
catalyst." I h' amines to form either the corresponding azeotropes or ammoni-
um formates.
From the reaction solutions of the rhodium-catalyzed hydro-
3.2.3. Hydrogenation of CO, in the Supercritical Phase genation of CO, in DMSO/NEt,. the formic acid formed can be
Carbon dioxide in its supercritical state is an interesting reac- recovered as sodium formate, with the noble metal being recov-
tion medium.[""^ 72bl and the possibility of transition metal cat- ered in catalytically active The liberation of formic
alyzed CO, activation in the supercritical phase was demon- acid from sodium formate is a well-known process, but involves
strated by Reetz et al., taking as an example the known synthesis ecological and economic problems that are intolerable today.
of pyroncs from alkynes and C02.[72c1 Jessop, Noyori, and Free formic acid can also be recovered from mixtures with
Ikariya recently reported that an efficient transition metal cata- amines by a number of processes based on reamination of the
lyzed hydrogenation of CO, to formic acid can take place in a formates and azeotropes to give thermally labile formic acid/
supercritical mixture of H,, CO,, and NEt, without any addi- amine adducts followed by distillative ~eparation."~' However.
tional solvent (Scheme 6).[731With the ruthenium complexes these methods can usually only be used on reaction solutions
after deactivation of the as formic acid would oth-
erwise decompose under the workup conditions. The loss of
Con (sc). Et3N costly noble metal that occurs and the laborious multistage
p"= 205 bar, T = 50°C workup and recycling processes are severe disadvantages of
H2 + CO2 * HC02H these methods. In addition to the search for even more effective
~(CI)2Ru(PMe3j41,
13a catalysts it seems therefore essential to develop cconomic meth-
ods for the recovery of the formic acid from the reaction solu-
TON = 7200
tions from CO, hydrogenation processes in 01-derto be able to
Scheme 6 Hgdi-ogcnation of C O , to formic acid in the supercritical phase accord-
ing to I - e l [73a] operate the process on an industrial scale.

3.3. Synthesis of Formic Acid Derivatives by the Hydro-


[(X),Ru(PMe,),] (X = CI, H) 13a and 13b, 7200 mol formic
genation of CO,
acid are formed per mol Ru with TOFs up to 1400 h - ' .
The reaction rate in the supercritical phase is 18 times that in
3.3. I . General Considerations
THF under comparable conditions. The authors assign this ben-
eficial effect to special properties of the supercritical phase with Under suitable reaction conditions. the hydrogenation of
respect to the miscibility and mass transport of the reac- CO, in the presence of aniines or alcohols can lead to amides o r
t:, t s, 17 3.11 esters of formic acid, respectively (Table 4). In most cases where
To ensure a homogeneous supercritical phase during the reac- experimental data are available, it is found that the formation of
tion. comparatively drastic reaction conditions are necessary derivatives proceeds by the intermediate formation of free
(205 bar total pressure. 50 'C). Rhodiurn(1) catalysts of the type formic "I although other reaction routes are pos-
used auccessfully in organic solvents and aqueous solution d o ~ible.['~'.". 791 The derivatization usually leads to products that

221 5
REVIEWS W. Leitner

Table 4. Catalytic systems for the synthesis of formic acid derivatives by the hydrogenation of CO,.

Entry Catalyst Solvent Reagent p( H )!P( CO 1 T Yield [a] TON [b] I Ref.
[bar] [ 'J ["/.I lhl

1 [Ir(PPh,),(CO)CI] benzene Me,NH ?X,'28 128 1200 17 [781


2 PdCI, NMP [c] MeiNH X0;40 170 YY 34 1.5 [79l
3 lRu(PPh,)+fH),l hexane Me,NH 30,'30 130 57 2648 6 1801
4 I P t , ( ~ c - d ~ ~ m[cl) , l toluenc Me,NH 114 (total) [d] 100 1378 24 [81 bl
8 [Ir(PPh,),(CO)CI] MeOH NH i 122 (total) [d] 128 - 1148 240 181c]
6 [Ru(PMe,),CI,I CO,,.', Me,NH [el 80/130 [d] 100 76 370 000 37 (78 a]
-
7 PdCI, MeOH MeOH 30: 30 100 38 10 [a31
8 IPd(dppe),l lcl EtOH EtOH 30:70 160 2 88 20 1841
-
9 [Fe,(CO),,Hl- MeOH MeOH 20QO 175 8.8 96 IS81
10 lRu,(CO),,(H),I- MeOH MeOH 17;17 125 7.3 24 [77a]
11 [(HC02)W(CO),]- MeOH MeOH 17/17 128 16.4 24 [77 bl
12 [Ru(PMe,),CI,I CO,,.,, MeOH 80.'128 [d] xn 12 3500 64 175bi

[a] Yield ofamide or ester based on amine or alcohol. [b] Maximum total number of mols formamide or ester per mol catalyst in the given reaction time. [c] NMP = N-me-
thqlpyrrolidone. dppm = Ph,P(CH,)PPh,. dppe = Ph,P(CH,)PPh,. [d] At reaction temperature. [el Used as dimethylammonium carbamate.

are stable in the presence of the catalyst at normal pressure, catalyst. H C 0 , H is formed in analogy to the system using tri-
although the thermodynamics for the formation of, for ex- alkylamines (Section 3.2.3).[731 Under the comparatively
ample, formamides are similar to those of formic acid. drastic reaction conditions (100 T, 210 atm), condensation of
dimethylammonium formate to D M F takes place in the liquid
phase. Most of the D M F formed then dissolves in the supercrit-
3.3.2. Synthesis of Formamides
ical phase, while the water content of the liquid phase increases.
As early as 1970, Haynes et al. synthesized dimethylfor- In this way, all the dimethylamine used is converted into D M F
mamide ( D M F ) from H,, CO,, and HNMe, by using transition quantitatively and with high selectivity. Small amounts of
metal phosphane complexes as the catalysts.[781Using the com- formic acid and trimethylamine (formed by further reduction of
plex [(Ph,P),(CO)IrCI]. they were able to obtain a total of DMF[*'".']) are formed as by-products.
1200 rnol D M F per mol catalyst by repeated use of the reaction
solution. In the years following, a number of other systems for 3.3.3. Synthesis of Formic Acid Esters
producing formamides from CO,, H,. and the corresponding
amines under similar conditions were described (Table 4) . [ 7 9 - 8 ' I The transition metal catalyzed formation of alkyl formates
The complex [(p-dppm),Pt,] (Table 4, entry 4) is exceptional, as from CO,. H,, and alcohols was first described by the Russian
it catalyzes not only formation, but also cleavage of DMF, de- research group of Vol'pin and K o l o m n i k ~ v .Not ~ ~ ~only
~
pending on the reaction Various other sec- phosphane complexes of transition metals of Groups 8-
10[54a.7 S b . 8 3 . 841, but also the carbonyl metalates of
ondary amines can be used, and the formation of formamide
itself in the presence of ammonia has also been reported.[*'1' Groups g [ * S , 7 7 ~ 1and 6 [ 7 7 b l show catalytic activity (Table 4). In
A very efficient method of synthesizing D M F is to use many cases, amines or other basic additives have a positive
dimethylamine as the amine component under conditions suit- effect on the course of the reaction.
able for hydrogenating CO, in a supercritical phase.[7sa1Using The anionic ruthenium carbonyl clusters used by Darens-
the catalyst [Ru(PMe,),CI,] 13a (Fable 4, entry 6). up to bourg et al. show considerably higher catalytic activity in the
370000 mol D M F per mol catalyst is formed in less than 37 h formation of alkyl formates by carbonylation of alcohols than
(Scheme 7). in the reaction of CO, with H, .(77a1 However, a possible reac-
tion route via the intermediate reduction of CO, to C O was
ruled out. In the presence of CO, and hydrogen, formic acid is
COZ(sc), MeZNH
formed initially, and then esterified under the reaction condi-
p"= 210 bar, T = 100°C tions.
Hz + GO, * HC(0)NMez
L(C1)2Ru(PMe3)41,13a
The formation of methyl formate by esterification of formic
acid obtained from CO, hydrogenation also takes place in the
TON = 370 000
supercritical phase if methanol is added to the reaction mixture
Scheme 7. Synthesis of DMF by hydrogenation of CO, in the supercritical phase
under conditions comparable to those in Scheme 6.[7sb3 Because
according to ref. [78:i].
of the high efficiency of the CO, hydrogenation under these
conditions, the yield of methyl formate exceeds the yields ob-
The solubility of the components of the mixture, which con- tained by the other methods. However, the esterification is in-
sists of two phases during the reaction, is of great importance for complete. and the reaction product consists of a 2: 1 mixture of
the high turnover numbers that are achieved with this system. formic acid and methyl formate.
The liquid adduct of dimethylamine and CO, (dimethylammo- Alkyl halides can be used instead of alcohols as the source of
nium carbamate, "Dimcarb"[821). which acts as the dimethyl- the alkyl groups for the formation of formic acid ester^.[^^.^'^]
amine source in the reaction in Scheme 7, is practically insoluble In this case, the derivatization most likely takes place directly on
in supercritical CO, because of its high polarity. In the an intermediate formate complex without the liberation of
supercritical phase. which contains CO,, H,, Me,NH. and the formic

221 6 Ariseii'. Clz~in.1111.Ed. Enzl. 1995. 34. 2207 -2221


CO, as ;I R a w Material REVIEWS
3.4. Mechanistic Aspects of the Addition of Hydrogen to
CO, with Formation of Formic Acid

3.4. I . General Considerations


The key step in the catalytic formation of formic acid or its
derivatives from CO, and H, is the formation of the formyl
C-H bond. In all cases in which catalytically active intermedi-
ates in the CO, hydrogenation to formic acid were characterized - J
spectroscopically, the formation of formate complexes was de-
tected in this ~ t e p . [ ~ ~ .C~arbonate
""~ ~ p e c i e s [ ~ ~and
, ~ 'metal-
] Rh
Pm, I l+
,#H
Rh
Solv' P'
lacarboxylic acids[6y1were also suggested as possible intermedi- Solv' 1'0
ates of CO, hydrogenation, and the formation of the C-H 16
HAO
bond by hydrolysis or hydrogenolysis of such intermediates can-
not be excluded a priori in spite of the lack of experimental
proof. f
The formation of the formate group on the metal center can HCOpH
take place either by the insertion of CO, into a M-H bond or t
by hydride transfer to coordinated CO,. A large number of
stoichiometric examples confirm the general validity of the CO,
Ps,, I l+
.,sH
Rh
insertion.l'h. -IS 861 and its exact mechanism is well understood in Solv' 1 'p
0 4
the light of experimental[86".8 6 b . 8 8 i and theoretical[*', I' inves-
H
tigations. Experimental evidence for the alternative pathway for 17
the formation of a forinate ligand. that is hydride transfer to Scheme 8. Catalytic cycle of the hydrogenation o f C 0 , with c'itionic rhodium coin-
coordinated CO,, has emerged only most recently in the oxida- plexes in THF according to ref. [55]. P = Me,PPh. S o h = solvent.
tion of [($-C,H,Me),M(CO)H] (M = Nb, Ta) to [($-
C,H,Mc),M(0,CH)]'87"1 and in the formation of [ ( I T ~ -
C,H,Me)(PCy,)Ru(q2-0,CH)] .[87b1 It should be noted, the monohydrido complexes formed are usually the more active
however. that CO, insertion cannot be definitely excluded to catalysts in hydrogenation reactions.[921Interestingly, the first
account for formate formation in both cases. example of an insertion of CO, into M-H bonds, discovered in
In this context, it is somewhat surprising that the insertion of 1968. involved a neutral monohydridocobalt complex, the ho-
C 0 2 into a Rh-H bond could not be realized for a long mologous 3 d metal to However, the reaction of
time(7.(r.h.911despite the excellent catalytic activities observed in neutral monohydridorhodium complexes with CO, in conven-
CO, hydrogenation using rhodium phosphane catalysts. It is tional organic solvents has been reported to lead to the forma-
only most recently that detailed information on the catalytic tion of carbonato or bicarbonato ~ o m p l e x e s . [74b,
~ ~ 911
" ~ Only in
cycle of the rhodium-catalyzed hydrogenation of CO, to formic the solvent DMSO, which is very suitable for catalytic hydro-
acid under various conditions has been collected. genation, was i t possible to observe by N M R spectroscopy not
only the CO, insertion but also for the first time all subsequent
steps of a catalytic cycle for CO, hydrogenation with the neutral
3.4.2. The Mechanism of the Rhodium-Catalyzed Hydrogenation hydrido complex [(Ph,P(CH,),PPh,),RhH] 18 (Scheme 9).[631
of C O , in Ovganic Solvents

Nicholas and Tsai used IR and N M R spectroscopy at elevat- H HC0,-


ed pressure to investigate the mechanism of formation of formic I
CO,, 1 atm
acid from H, and CO, in T H F with the catalyst
[Rh(Me?PPh),(nbd)]BF, in the absence of a m i r ~ e s . " ~They~
were able to demonstrate the formation of the cationic dihydri- 18
d o complex 14 and the subsequent insertion of CO, into the [D6]-DMS0, T=22 "C
Rh-H bond to give complexes 15 and 17 with respectively q l -
or ?/'-bonded formato ligands (Scheme 8). Only the y 1 complex
15 appears to be actively involved in the catalytic cycle. The
subsequent step of reductive elimination of formic acid to give
the square-planar cation 16 and regeneration of the dihydride 14
by oxidntivc addition of H, were postulated in analogy to
known reactions.
It would appear likely at first sight that this mechanism could
also be applied to the considerably more effectively catalyzed
hydrogenation of CO, to formic acid by rhodium phosphane 20
complexes in DMSO/NEt, . However, cationic dihydrido com- SchemeY. Reaction of [(Ph2P(CH,),PPhl),RhH] 18 %it11 U12 and H2 in
plexes like 14 are deprotonated in the presence of amines, and [DJDMSO accordins to ref. [ 6 3 ] . P = PPh,.

2217
REVIEWS W. Leitner

Formal insertion of CO, into the Rh-H bond of 18 leads to ly prepared and characterized by X-ray crystal analysis by
the complex 19, which, unlike all other known transition metal Werner et a1.'"61 Starting from 21, the catalytic cycle in
formato complexes exists in dissociated form in solution. Never- Scheme 10 can be closed by the oxidative addition of hy-
theless, the insertion is reversible, as shown by the rapid CO, drogen and reductive elimination. The bicarbonato complex
exchange and incorporation of deuterium in the formate unit. [(H)2Rh(iPr,P),(qZ-0,COH)] related to 22 was characterized
Interestingly, the rates of these exchange reactions with com- by Ibers et al. by X-ray structural analysis.[74h1
plex 19 and its analogue bearing the phosphane ligand Sakaki et al. have have carried out theoretical studies on the
Ph,P(CH,),PPh, reflect the catalytic activity of the correspond- CO, insertion into the Rh-H bond of [(PH,),RhH] and found
ing hydrido complexes in the hydrogenation of CO, .[h31 The that coordinated formate is formed and bound in a q'fashion
oxidative addition of H, to the cation of 19 yields the dihydride owing to the presence of three additional phosphorus lig-
20, which is in equilibrium with the monohydride 18 and free and^.['^'] Very recent a b initio calculations by Dedieu et al. show
formic acid under the reaction conditions given in Scheme 9. that the q2 formate group represents the most stable coordina-
However, complex 18 is only a moderately active catalyst for tion form in the presence of only two P donor atoms as depicted
the hydrogenation of CO,, as it contains two chelating phos- for complexes 21 and 22 (Scheme 10).["71However, it appears
phane ligands per rhodium center.[57.6 3 1 The catalytic cycle of from this latter work that the q' form is the more reactive species
Scheme 9 can be applied, however, in an analogous manner to which sustains the catalytic cycle. Most intriguingly. the study
the most active catalyst systems in which the ratio Rh/P, is 1 :1 by Dedieu et al. points to an interesting alternative for the liber-
(Scheme The starting point for the catalytic cycle is now ation of formic acid from formate complexes like 15 and 21.[971
the hydrido complex 11, which can be formed from all A a-bond metathesis between the q 1 formate group and non-
the catalyst precursors so far used under these conditions classically coordinated H,['*] seems feasible to by-pass the oxi-
(Scheme 4).[57.581 dative addition/reductive elimination sequence. The Rh-H
bond required for the insertion of CO, is regenerated without
changing the oxidation state of the metal center, and the calcu-
lated energy barriers for the o-bond metathesis are considerably
less than those of the mechanisms shown in Schemes 8 and 10.
It should be noted that the oxidative addition of H, has so far
only been demonstrated experimentally in the catalytic cycle of

Y
HCOzH
Scheme 9. where a o-bond metathesis is impossible.
Furthermore, it is interesting to note that the two mechanisms
of Scheme 8 and Scheme 10 differ not only in the charge and
coordination number of the intermediate species. but also quite
fundamentally in the order of events. Whereas in Scheme 8 the
product-forming step takes place immediately after reaction
with CO,, in Scheme 10, product formation follows the reaction
with hydrogen. One might speculate on the impact of this situa-
22 tion on the large difference observed in the activity of the two
H2
Scheme 10. Application of the cycle in Scheme 9 to the most active catalyst systcm
catalytic systems. Although questions of detail require further
dppb;'Rh with a ligand-metal ratio of 1 . 1 according to ref. [57]. P = PPh,. experimental investigation, we may conclude that the two mech-
anisms depicted in Schemes 8 and 10 present a clear and reliable
picture of the actual catalytic cycle of the rhodium-catalyzed
Electronically unsaturated 14e complexes like 11 were stud- hydrogenation of CO, to formic acid under the individual reac-
ied in detail by Muetterties et al.[941and by Fryzuk et They tion conditions. Building on the reaction mechanism proposed
tend to form hydride-bridged clusters [{ (P,)Rh(p-H)),J ( n = in Scheme 10, it was already possible to develop catalysts whose
2-4), and both the monomers and the intact clusters can take activity exceeds that of the original in situ systems by more than
part in catalytic The participation of bridged hy- an order of magnitude (Scheme 4).[57.581Catalytic cycles for
dridorhodium clusters has to be taken into account for CO, formic acid formation from CO, and H, involving metal centers
hydrogenation, as insertion of CO, into a R h - H bridge is a other than rhodium have not yet been studied in great detail and
known process.[95]However, there is so far no experimental it will be interesting to see what kind of general pattern will arise
evidence for the involvement of oligomeric species in the catalyt- from future studies.
ic cycle of the rhodium-catalyzed hydrogenation of CO, .[64a1
It is reported that for the rhenium complexes [Re(bpy)(CO),H]
and [(p-H)(Re(bpy)(CO),},]+, CO, is inserted into the Re-H 4. Summary and Outlook
bond of the monomeric complex only, the reaction being
stoichiometric." "I The reduction of CO, to formic acid and its derivatives can be
Insertion of CO, into the Rh-H bond of I 1 can produce a carried out by photochemical and electrochemical processes as
formate group in analogy to the model complex 18, but the well as by the direct addition of H,. Transition metal complexes
formate group acts as a coordinating ligand in 21 owing to the have been found to catalyze all these routes. With regard to the
electron deficiency of the catalyst center. The q2-carboxylato reduction of CO, by electron transfer, recent years have seen a
complex [ (iPr,P),Rh(q2-0,CCH,)] analogous to 21 was recent- growing understanding of the catalytic cycles that comprise the

221 8 A n ~ e i t Chrm.
. In(. Ed. Engl. 1995, 34, 2207-2221
CO, :IS ;I R a w Material REVIEWS
competing rctiuction processes that lead to the formation of (Eds.: B. P. Sullivan, K Krist. H. E C;u:id). Elsc\icr. ."uii\terdam. 1993:
f ) M.M l%alm:iiin,Cli?iiiicu/ F i y o r i o i i of Crirhoii L)i(i.iifl?. ('KC. Hoca Raton.
HC'O;. CO. and H,. Taken in conjunction with the enormous 1993: g ) C'iirhoii nioi-iili,C'/iiwiis/ri.: E i i r i r i ~ i i i i i i ~ i i l/ \[,i! il t ( , . \ ( E d s : J. Paul. C:M.
number 01' possible combinations of catalysts with electron Pradicr), Royal Society of Chemistry. London. 1994.
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I') P. Braunitein. D. Matt. D. Nobel, Choii. Rci,. 1988. SS. 747: g) I.S. Koloni-
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Even inore so because even today very effective catalytic systems I Toinmm. ~ V i wJ. Choir. 1994. / X . 133: k ) P. G . Jessop.'I'. Ikoriyn, I<Noyori.
Cliiwi. R ~ Y1995, 'IS. 259; I ) W. Leitner. C i w d ( ' h i l<c>! in p r e %
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;I judicious use of "thermodynamic tricks". which enable high C ' l i c w . Eli,? :Veils 1991. /5'1(13), 7 . c ) J. L . Sarnmicnto. i h i i l 1993. 7/(22). 30: d )
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Turner i n ref. [2g]. p. 317.
ergic nature of this reaction under standard conditions. Equally See for exiimple: a ) 7%c Hoiidhuok of ~ i i i , ; r i i i i i i i i , i i r i i lC'Ii<wii.\rri~.I ul / , Purr .4
important i h the rapid progress in our understanding of the (Ed.: 0. HutLinger). 1st ed.. Springer. Berlin, 1980: b) R . Ktimmcl. S . Papp.
L : i i i i l e l r i ~ h o i i i ~ , .2nd cd , V E B Deutscher Vtrlitg I h r (;riiiidsturlifindustrie.
fundainental mechanisms of catalysis based on experimental
Leipig. 1990. c ) C -D. Schonwiesc. B. Diekmann. I k r 7reih/ioii
and theoretical studies that has a continuing influence on the : L f e i i s i It l-o-iiiidwr rlu.\ Kiiiitu, Rowohlt. 1990: d ) W. Seilritr. I)rr

development of' new and powerful catalysts. Both the turnover / c k / . Hanser. Munchcn. 1991.
a ) Grwidiousc Gm Eiiii\,sioii,v /roiii Power Sruriim. IEA Gi-ceiiliousc Gas R & U
numbcrs and turnover frequencies of these catalytic systems can Programme. Cheltenham. 1993: b) C'urhoii Dio wli, C ' u p r i m Froiii /'un.o. S r i i -
compete with those of other homogeneous transition metal cat- t1oii.s. IEA Greenhouie Gas R & D Programme. Cheltcnliaiii. 1994.
K i r k - 0 t l i i i i e r E i i z y d q t i 4 ( i of C'hiviiiciil Tcdiiiuliigi'. ciil 5. 4th rd..Wile). New
alysts that arc already used on an industrial scale.
York. 1993, p. 35.
The principles explained in this review for the hydrogenation Mi~rA/i/iirier, y / i i l i r / i c / i e.Arhcir\.v/o/fc iKiihn-Birr.rr i , 1oi .Y. 9th rd.. cconied.
o f C O , can ;11so be applied in full analogy to the simultaneous Landsbeig. Lech. 1990.
Riiiiip~~ Clieiiiic Li,.\-ih-oii (Eds.. 1. Falbe. M Regitr). 0th c d i l i o i i . Thiemc. Stutt-
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A I I , ~ ~ '('Iii2ni.