Académique Documents
Professionnel Documents
Culture Documents
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.
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
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)
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.
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
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-
Table 3. Catalytic systems for the synthesis of formic acid oi- formates by the hydrogenation of CO,. RT = room temperature.
[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.
221 3
REVIEWS W Leitner
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-
[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[.
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
[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
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.
s o ~ ~ r c etsh.i \ should lead to a rapid and fruitful growth in this a ) D. J Darensbourg. R. A. Kudaroski. Adl-. O r p i i o n i t , / ( ' I i m 1983. 2 . 129:
h) D. R.Palmer. R van Eldik, C'/i~,iii. Kci. 1983. 83. 651 . c ) D. Walther. C'oorrl.
area (%em K c r . 1987. 7'1. 135: d) A Behr, A i i g w Chriii. IY8X. /OO.6x1: A i i g w .
However-. in the medium term, the use of hydrogen for the C ' l i c i i i , Irir. Ed. D i , q / . 1988. 27. 661 ; C) A.ywcr\ H i i i i i i l , ~ ( , i i ~ , , C'ci/iil.
,ii~ 1988. 6. 59:
I') P. Braunitein. D. Matt. D. Nobel, Choii. Rci,. 1988. SS. 747: g) I.S. Koloni-
reduction 01' CO, to formic acid is certainly a more easily real- nikov. T. V. Lysak. Rii.s.5 C/iivii. R1.r. I G i g I . 7i.iiii.\/. ' 1990. 59, 344: 11) D.
ized approach. as it is based on existing technical know-how. Wnlther. ,Yoc/ir. C ' / i w i . 7iw'i. Luh. 1992. 40. 1214. i) M Arejta. E Quartana.
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 %
for this reaction are already available. This is partly a result of See for example: 'I) E. T. Suiidquist, S c w i c r 1993. 239. 934. b) P S. Zurer.
;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 )
yields o f reduction products to be obtained in spite of the endo- U . Siegentlialer. J L Sarmiento. .Yoriirc 1993. 36.5. 119. c ) t) Dyinwn. D. R
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-
activation of C O , and any X-H bonds. As can be seen from
g u t . 1990. p. 2277
Equation ( o ) ,the thermodynamic conditions that apply, for ex- Haiid/Jllok 01 CIi?iiii\rrv u i i d Physic$. (Ed.: R . <'. LVciist). C'RC. 65111 cd.. Boca
Rntoii. 1984.
a) A Y. Rormhky. kiiicr. Cuiul 1980. 21. 97: h) G C. Chiiichrii. P. J. Denny.
D..I Parker. M . S. Spencer, D. Whan. A p / d Curd. 1987. 30. 333: c) G C.
C'hiiichen. K . Manlicld. M S. Spencer. C H E M T E C H 1990. 6 Y 2 : d ) K. C.
Waugh. C u r d . Tc~dm1992. t.5. 51
1 'lliiiuiiii '\ Eii:i~dqiidiu of Intliisrrid Climii.wi, 5th ctl.. VCH. Wciiiheim.
ample, to the reaction of methane with CO, to form acetic acid 1986.
S. Rajagopal. M.K Aiiwcr. A. F. Spatola. ~l,)Jrld?.51994. 1 I
are comparable to those for the formation of formic acid iic- For the application of formic acid i i b hqdrogeii donor in ~iiiintiiiselecti\ehy-
cording to Equation (n). Possible single steps in a potential drogcnation see a) H Brunner, W Leitner. . 4 i i g i w ( l i m i t 1988. 100. 1231:
A i i , ~ c wC ' l i m i . h r . E d OigI. 1988. 27, 1180: b) h! Lcitiier. _I M . Brown. H
catalysis cycle such as oxidative addition of C-H bondsl"' or
Brunner. .I A i i i . C'lieiii. Soc. 1993. 1t.i. 152.
insertion o f C 0 2 into M-C bonds[2h.3 . 862'1 are also known. The F Lippert. A . H d i n (BASF AG). EP 583695. 1994 [Cliiwi .A/nfr.1994. 120.
creativity and inventiveness of many dedicated chemists will be 21 6715fJ.
I. Willner. B. Willncr. Top Ciirr. C ' h i i i . 1991. / j Y . 15.3
needed t o p i t together the pieces of the mosaic. but achievement a ) J. Hiiweckcr, J-M. Lehn. R . Ziesel. l l c l i , . Cliini. . A ~ r o1986. 6Y. 1990: h ) J. P
of the iiltimnte aitn will fully justify the effort Collin, J. P. Sauvage. Coorri. C h i . Riv. 1989. Y7, 245: c ) M lH.immoucht. D.
L e u . M. Momenteau. JLM. Siivknt. J. Aiw. C h i . . S i r . 1991. //.?, X455: d) C i .
SiILcstri. S. Garnbino, G. Filiirdo ti1 ref. [2d]. p. 101: c ) I R . Kcenr. B. P.
S u l l i u n in ref. ['el. p. 1 1 X
J.-P Collin. A. Jouati. J.-P. Sauvagc. I i i o r j i . C h i . 1988. 2-. I W h .
M. Tezuka. 7. Yajiiiia. A . Tsuchij;~.Y Matsuniotu. Y Uchid;i. M . Hidai. .I Ani.
C'/ii,iii. So< 1982. 104. 6834.
M. Nakarawa. Y Mirobe, Y.Matsumoto, Y Uchida, M . Tcruka. M. Hidai.
Biill. C . / i u i i . Soi.. J p i . 1986. SY. 809.
T. Tomohiro. K Uoto. H. Y Okuno. J C ' l i w i . Sort C ' h c i i i . ( ' o i i i i i i i i i i . 1990. 194.
K Tanaka. T Matsui. T 'Panaka. .I h i . C lw ii. S m . 1989. / I / .376s.
H . Ishida. H. Linaka. K. Tan;ik;i. T Tiinaka. J. C h m . , S O ( . C l i m . C ' o i i i i i i i i i i .
1987. 131.
a) M. R M. Bruce. E. MeGehce. B. P.Sullivan. FI Thorp. I R O'Toolc. A.
Downiird. T, .I. Meyer. Orjiuiioii?i~rril/ii~\ 1988. 7 . 23X: h ) M I<M . Brucc. E.
MeGehee. B. P. Sullivan. H. H Thorp. T. R. O'Toole. A. Do\iiiard. J. R Pugh.
T. J Meyer. Iiiorg. C'liiwi. 1992. 31. 4864.
a) S. Slater. I H. Wagrnknecht. 1 h i . Cliivii. S o l . 1984. /06. 5307: h ) A.
Srymasrek. F P Pruchnik. J. Or,i?oiioiiier. ( h i i . 1989. 376. 133.
S.Ramiursen. M . M Richter. E. YI. H. Place, K.J. Brewer. Iiiuiy C h i i 1990.
29. 3926.
a ) C. M . Bolinger. 8. P S u l h a n . D. Conrad. J. A Gilbert. N. Stor). T. I .
Meyei-. J. C'heiii. Snc. C . h o i ? . Coiiiiiiiiii. 1985. 796:b) C M.Hcdinger. N.Story.
B. P . Sullivan, T. J. Meyer. I i i i w g Cliwi. 1988. 17.4581.
T. Yoshida. K Tsutumidn. S. Teratani. K Yasufuku. M . Kaneho. ./. C / i m Six.
( Y i m i i . ( ' o i i i i i i i i i i . 1993. 631
a ) S . Kapusta. N . Hackrrman. J Elwrroclicrii. Sui. 1984, lil. 151 1: b) M. N .
Mahniood. D Masheder. C J. Harcy. ./. Appl. t l w r r o f h r v i i 1987, 17, 1233:
c ) N. Furuya. K . Matsui. J. El~wruuiiul.Chmi. Iiircrfoiiul Elvi r r i i ~ ~ l i c ~1989. iii.
2 7 / . 1x1: d) N . Furuya. S. Koide. Eiectvocliim. A i t u 1991. 3h. 13U9.
H . c' Hurrell. A. L. h4ogst;id. D. A . Usifer. K . T. Pott'l. H. D. Abrutia. / i i w g .
C'/?lWi. 1989. 28. 10x0.
2219
W. Leitner
REVIRNS
[31] T. Yoshida. T. lida. T. Shirasagi, R.-J. Lin. M. Kaneko. J. Elwrrounul Chcm. (5x1 a ) R. Fornika. Dissertation. Universitit Jena. 1994; b) R. Fornikn. H. Girls.
Inrrii/uciu/ E/ec/rocheni. 1993, 344, 355. B. Seemann, W. Leitner. J. Chem. Six Chm. Comwurrr. 1995. 1479.
1321 H . Ishida. K. Tanaka. T. Tanaka, Orgunoinc/u//ics 1987. 6. 181 [59] a ) K. Wagner. Angei~~ C k i m 1970. 82. 73: dngctv. Chent. I n r . E d Engl. 1970.
1331 a ) H. Ishida. H. Tanaka, K . Tanaka. T. Tanaka, C h e n ~Lerr.
. 1987, 597; b) H. Y. 50: b) K. Narita. M. Sekiya. Chem. Phurm. Bull. 1977, 25. 135.
Ishida. K . Fujiki. T. Ohba. K. Ohkubo, K. Tanaka, T. Terada. J C'hern. Sor. [60] a) W. Leitner, P r o < . 11. I n [ . Con/. Curhon Dio.rirk LitilixUion. Bari 1993, p. 113 ;
Dulron Trans. 1990. 2155: c) M.-N. Collomb-Dunand-Sauthier,A. Deronzier. b) E. Graf. W. Leitner. C%cwr.Err. in press.
R. Ziessel. Inorg. Chenr. 1994. 33. 2961. (611 21) M. M. Rahman, H. Y. Liu, A. Prock. W. P. Giering. Orgrr~tot~ictullir~.~ 1987.
[34) a ) J. Hawecker. J.-M. Lehn. R. Ziessel, J. Chem. Soc. C/icm. Cunrnii~n.1984. 6 . 650: b) R. C. Bush. R. J. Angelici. Inorg. Chm. 1988.27. 6x1; c ) J. R. Sowa.
328: b) B. P. Sullivan, C. M. Bolinger, D . Conrad. W. J. Viiiing. T. J. Meyer, R. J. Angelici, ihid. 1991, 30, 3534.
ihid. 1985. 1414: c) G. Calraferri. K. Hidener. J. Li, J. P h o r a c h ~ n P~ h. o r o h d . A (621 a) C . A. Tolman. C'h~~m. R e . . 1977, 77. 31 2: b) T. L. Brown. Inor,q. Chcni. 1992,
1992. 64, 259; d ) P. Christensen. A. Hamnett. A. V. G. Muir. J. A. Timney. 31. 1286.
J. Chr~ni.So(.. Drrlrorr Trons. 1992. 1455. [63] T. Burgemeister. F. Kastner, W. Leitner, Angcw <'/rein. 1993, 105. 781; Angew.
1351 a) C. R. Cabrera. H. D. Abrufia. J. Eledruunul. Chpm. Inrrufucial Elemwhcm. C'hmw. l i t f . Ed. E q / .1993, 32, 739.
1986. 2OY. 101: b) S. Cosnier. A. Deronzier. J.-C. Moutet. J. Mid. Cutal. 1988, [64] a ) R. Fornika. E. Dinjus. H . Gorls. W. Leitner. J. Orgunomet. Chc~rn.in press:
45. 381 : c) T. R. OToole. B. P. Sullivan. M. R. M. Bruce. L. D. Margerum, b) F. Gassner. E. Dinjus. H. Gorls. W. Leitner. unpublished results.
R. W. Murray. T. J. Meyer. J. Nrcrrocinul. Chmi. Irirrufuciul Elecrrochent. 1989. [h5] a ) M. D. Fryzuk. Cun. J. Chem 1983, 6 / . 1347; b) M. D . Fryzuk, T. Jones.
25Y, 217. F. W. B. Einstein, Or,~u~rrnot~i~~tulli~:v 1984, 3, 185: c) M. D. Fryzuk. W. E. Piers.
(361 a) N . D. Silavwe. A. S. Goldman. R. Ritter. D. R. Tyler. Inorg. Chrm. 1989.38, S. J. Rettig. F. W. B. Einstein. T. Jones. T. A. Albright. J. Am. Chrm. Soc. 1989,
1231; b) D. A. Morgenstern. R. E. Wittrig. P. E. Fanwick. C. P. Kubiak. 111. 5709: d) M. D. Fryzuk. W. E. Piers, F. W. B. Einstein. T. Jones, Cun. J.
J. An?. Cheni. Soc. 1993. 115. 6470. Chvit?.1989, 67. 883.
(371 N. S. Lewis, G. Shreve in ref. [2e], p. 263. [66] a ) A. A. Oswald. D. E. Hendriksen, R. V. Kastrup, K . Irikura. E. J. Mozeleski,
(381 a) M. Halmann. Nulure 1978. 275, 115: b) A. Henglein. M. Gutierrez. H. D. A. Young, Pho.sphorirs Siilfiir 1987, 20, 237; b) A. A. Oswald, D. E. Hen-
Fischer, Ber. Buns~n-Gc.~. Plrys. Chrm. 1984. 88. 170; recent examples: c) H. driksen, R. V. Kastrup. E. J. Mozeleski in Homogiwuus Trunsirion Mrrul Cut-
Inoue, T. Torimoto, T. Sakata. H . Mori. H. Yoneyama. Chwn. Lcrf. 1990, 14x3: u/yied Reui /;(JKY (Adv. Chem. &'. 1992. 330, 395).
d) H. Noda. A. Yamamoto. S. Ikeda. M. Maeda. K. Ito. ihid. 1990,1757;e) H. 1671 K. Kudo, N. Sugita, Y Takezaki. Nippon KuRuku Kui.shi 1977. 302.
Kisch, G. Twardzik. Chmi. Ber. 1991. 124. 1161; f ) J. F. Liu. C. Y. Baozhu, (681 C. J. Stadler. S. Chao. D. P. Summers. M. S. Wrighton, J. Am. Chem.Sor. 1983,
J Elrcrrounul. Chein. Intrufuciul Ekctrireheni. 1992,324. 191 ; g) M. Kanemoto. 10.7, 6318.
T. Shiragami. C. Pac. S. Yanagida. J, P/i?..s. C'hem. 1992. Y6. 3521, h ) M. 1691 a) M. M. Tiiqui Khan, S. 9 . Halligudi, S. Shukla. J Mu/. Curd. 1989. 53. 305:
Kanemoto, M . Nomura. Y. Wada. T. Akano. S. Yanagida. Chon.L r f f .1993. b) ;hid 1989. 57. 47.
1687: i)S. Ikeda, A. Yamamoto. H. Noda. M. Maeda. K. lto. Bull. Ciiem Soc [70] a ) R. Girtiier. B. Cornils. H. Springer, P. Lappe (Ruhrchemie AG). D E
Jpn. 1993.66, 2473: k) M. Halmann. B. Aurian-Blajeni. J. Ele~trourzu/.Citrnt. 3235030. 1982 [Chmz. Ahsrr. 1984, 101, 55331 t]; b) L. Bexten. B. Cornils, D .
lit/ru/uciu/ E/ivrrochcni. 1994, 375. 379: I) C. Furuya (Tanaka i d ) . J P Kupies (Ruhrchemie AG). D E 3431643. 1984 [Chmnt. Ahsrr. 1986. 105.
6158374. 1994 [Chem. Ahsrr. 1994. f21, 182382~1. 117009nj: c) W. A. Herrmann. C. W. Kohlpaintner, Angel<. Chmi. 1993. 105.
[39] a) B. A. Parkinson. P. F. Weaver. N u r i m 1984. 309, 148; b) S. M. Aliwi. 1588: Angrii,. Chern. I n / . EL/.Eng/. 1993. 32. 1524.
I . Al-Daghstani. J. Sol. En'nrr,?j Rex 1989. 7,49: c) S. Chao. C . J. Stadler. D. P. 1711 a) F. Gassner, W. Leitner. J Chmn?. Soc. Chm. Cormnun. 1993. 1465: b) F.
Summers, M. S. Wrighton, J Am. Chem. So(. 1984. 106.2732: d ) M. Wrighton, Gassner. Dissertation. Universitit J m a , 1994.
J. Vuc. Set. Tech. A 1984. 2. 795: e) 2. Goren. I. Willner. J Phys. Chin. 1990, 1721 a ) G. Kaupp. An,q,ii. Chon. 1994, 106,1519; Angew. Chem. I n / . Ed. EngI. 1994.
Y4. 3784: f ) P. Albers, J. Kiwi, N c i v J. Cheni. 1990. 14, 135: g) K. Hirano, 33. 1452: b) M. Poliakoff. S. G. Kararian. S. Howdle. ihid. 1995, 107,1409 and
K. Inoue. T. Yatsu. J. Photocheiti. Photohiol. A 1992,64. 255; h) M. Takayuki. 1995. 34. 1275: c) M. T. Reetz. W. Konen. T. Strack. Chiniiu 1993, 47. 493.
H . Tsutumi. K. Ohta. A. Saji. H. Noda, Chert?. Lctr. 1994. 1533: i) V. Heleg. 1731 a) P. G. Jessop. T. Ikariya. R. Noyori. Nururr 1994, 368, 231; b) T. Ikaraiya.
1. Willner. J. Chein. Sue. Chrni. Cominun. 1994. 21 13. P. G. Jessop. R. Noyori EP 652202. 1994.
[40] M . T. Khan, N. N. M . Rao, D. Chatterjee. J. PAorochen~.Phorohiol. A 1991. (741 a ) S. Krogsriid. S. Komiya. T. lto. J. A. Ibers, A. Yamamoto. Inorg. Cltrw~.
60, 311. 1976. 15. 2798: b) T. Yoshida. D. L. Thorn, T. Okano, J. A. Ibers. S . Otsuka.
[41] S. Matsuoka. T. Kohauki. C. Pac. A. Ishida, S. Takamuku. M. Kusaba. J. Am. Chr'in. Soc. 1979. 101,4212: c) L. Dahlenburg, C. Prengel, J. Ogunomer.
N . Nakashima. S. Yanagida, J. Phys. Clieni. 1992. 96, 4437. Chc~rii.1986,308.63:d ) L. Dahlenburg. C. Prengel. N. Hock. Z . Nrrrur/orsch. B
[42] a) D. Mandler, 1. Willner, J. A m . Chrm. Sue. 1987, 109. 7884: b) I . Willner. 1986, 41. 718.
D. Mandler. ihirl. 1989, 111. 1330. [75] a) P. G. Jessop, Y Hsiao, T. Ikariya, R. Noyori. J. Am. Chem. Soc. 1994. 116,
1431 a) S. Matsuoka. K . Yamamoto. C. Pac, S. Yanagida. Clr~~rn. Lefr. 1991, 2099; X851 ; b) J Cheni. Soc. Cheni. Commim. 1995, 707.
b) S. Matsuoka, K. Yamamoto, T. Ogata, M. Kusaba. N. Nakushiind. [76] a ) J. J. Anderson. J. E. Hamlin (BP Ltd.), EP 126524. 1984[Chein. Ahstr. 1985.
E. Fujita, S. Yanagida, J. An?. Chrin. Suc. 1993. 115. 601; c) T. Ogata, Y. 102. 95259~1;b) J. J. Anderson. D. J. Drury, J. E. Hamlin. A. G. Kent (BP
Yamamoto, Y. Wada. K . Murakoshi, M. Kusaba, N. Nakashima. A. Ishida. Ltd.).WO2066, 1986(Chem. Ahstr. 1986, l05,210757q]:c)M. J.Green,A. R.
S. Takamuku. S. Yanagida, J. P/iy.s. Clieni. 1995. Y. 11916: d ) T Ogata. S. Yana- Lucy, M. Kitson, S. J. Smith (BP Ltd.), EP 329337, 1989 [ C h m . Ahsrr. 1990.
gida. B. s. Brunschwig. E. Fujita, J. A m . Cheni. Soc. 1995, 117. 6708. I f ? . 58742rl; d ) R. G. Beevor. D. J. Gulliver, M. Kitson. R. M. Sorrel1 (BP
[44] M.-N. Collomb-Dunand-Sauthier. A. Deronzier. R. Ziessel, J. Orgunumer. Ltd.). EP 357243. 1989 [Chr,m. Ahstr. 1990. 113, 114638~1;e) D. C. Engel.
Chrm. 1993, 444, 191. W. P. van Swaji, G . F. Versteeg (University Twente). EP 597151. 1994 [Chem.
[45] N. Kitamura, S. Tazuke, Chent. Lerr. 1983, 1109. Ahsrr. 1995. 122, 5 8 8 1 4 ~ ) .
[46] a) J. Hawecker. J.-M. Lehn. R. Ziessel. J. C%en?.Snc. Chem. Conimurr. 1985, 56; [77] a ) D. J. Darensbourg. C. Ovalles, M. Pala, J. Ant. Chcvn. Soc. 1983. 105. 5937:
b) R. Ziessel in ref. [2g], p. 79: c) J.-M. Lehn. R. Ziessel. J. Orguiromet. Cheni. h) ;hid 1984. /06, 3750: c) ihrd. 1987, IOY, 330.
1990.382, 157. (781 P. Haynes. L. H. Slaugh, .1. F. Kohnle. Trtruherlron Lrjtr. 1970, 365.
(471 a) H . Ishida, K. Tanaka. T. Tanaka, CIzeni. L e t r . 1987, 1035; b) ;/JILL 1988. 339; [79] a) K. Kudo, H . Phala. N. Sugita. Y. Takezaki, Chcin. Lert. 1977, 1495;
c ) H . Ishida. T. Terada. K . Tanaka, T. Tanaka, Irrorg. (%em. 1990. 29. 905. b) H. Phala. K . Kudo. N. Sugita. Bull. Insr. Chtvn. Rrs. K w r o Uniu. 1981,
[48] C. A. Craig. L. 0 . Spreer, J. W. Otvos. M. Calvin. J P/I,I..\. C/ieni. 1990. Y4. 59, 88.
7957. (801 Y. Kiso. K. Saeki (Mitsui Ltd.). JP 36617, 1977 [Cheni. Ahstr. 1977. 87,
[49] a) S. M . Aliwi. J. Pho/ochetn. Pholohio/. A 1992. 67. 67: ;hid 1992. 67. 329. 84562~1.
[SO] J. R. Pugh. M. R. M. Bruce. 9. P. Sullivan, T. J. Meyer. Inor,?. Chiw. 1991. 30. [XI) a) S. Schreiner. J. Y. Yu, L. Vaska, J Cheni. Sac. Chen?.Comrnun. 1988, 602: h)
86. Inorg. Chbn. A</// 1988. 147. 139: c) L. Vaska, S. Schreiner, R. A. Felty, J. Y.
[SI] H . Tanaka, H. Nagao. S.-M. Peng. K. Tanaka. Orgunomcru/li~s1992. 11, 1450. Yu. L Mol. Curul. 1989. 52. L11.
1521 8 . Jeaowska-Trzebiatowska. P. Sobota. J. Orgunumer. Cheni. 1974. NO. C27. [XZ] a ) J. A. Mitchell. E. E. Reid, 1 Atti. Chrin. S r r . 1931. S3. 1879; b) W. Schroth,
1531 a) Y. Inoue, H . Izumida. Y. Sasaki. H. Hashimoto. Chcwri. Lerr. 1976. 863; J. Anderwh. H.-D. Schidler, R. Spitzner. C'li~wt.Ztg. 1989. 113. 9.
h) M . Sakamoto, I . Shimizu. A. Yamamoto. Orgorionirtullic.\ 1994, /3,407. 1x31 a ) 1 S. Kolomnikov. T. S. Lobeeva. M. E. Vol'pin, h. Akud. Nuuk. Sep. K/zrm.
[54] a) Y. Hashimoto. Y. Inoue (Mitsubishi Co ). J P 138 614, 1976 [Chcm. Ahstr. 1970, 2650; b) T. S. Lobeeva, M. E. Vol'pin. ihrtl. 1972. 2329.
1977. 87, 67853~1:b) T. Yamaji (Teijin Ltd.). J P 166 146. 1981 ( C % E I ~ .Ahstr. (841 Y. Inoue. Y Sasaki. H. Hashimoto, J Chcm. Sot,. Chmi. Cnminun. 1975. 718.
1982, Y6, 1222114: c) T. Yamaji (Teijin Ltd.). J P 140948, 1981 [C%cm.Ahstr. [CCS] G. 0. Evans. C. J. Newell. Inorg. Chin?.A(,tn 1978. 31, L387.
1982. 96. 68352dl; d) D. J. Drury. J. E. Hamlin (BP Ltd.). EP 95321. 1983 [X6] a ) J. D . Miller in Rrucfi(m.\ of Coorrlinuferl Ligund.s, Vo/. 2 (Ed.. P. S. Brater-
[Chrrn. Ahstr. 1984. 100, 174262kj: e) A. G. Kent (BP Ltd.). EP 151510. 1985 man). Plenum. New York, 1989, p. 1 , b) D. J. Darensbourg in Lit. [2d].
[C'hcm. Ahsrr. 1986. 104. 109029hl: f) C. P. Lau. Y Z. Chen. L Mol. C i r t a l . A p. 43: recent examples: c) ref. [SO]: d) K . K . Pandey, K. H. Garg, S. K.
C'hern. 1995, 101. 33. Tiwari. Po/h&nn 1992, 947: e) J C. Berthet. M. Ephritikhine. New J. Cheni.
1551 L C . Tsai. K. M. Nicholas. J. Am. C/ii~m. So<,.1992. 114. 5117. 1992. 16. 767; f) D. Nietlispach. H. W. Bosch. H . Berke. Chern. Ber. 1994. 127.
[56] a ) E. Graf. W. Leitner. J. C/ton. S o < .Chivii. C'ommrin. 1992. 623: b) W. Leitner, 2403.
GIT Fuchz. Luh. 1992, 36. 912. 187) a) P.-F. Fu. A. K. Fazlur-Rahman. K . M. Nicholas. Orgunomi~/u/hc.s1994. 13.
1571 W. Leitner. E. Dinjus, F. Gassner, J, Orguriomet. C%em. 1994. 475. 257. 413: b) C. S. Yi. N. Lin, !hid. 1995, 14. 2616.
[92] a) R . R. Schrock. J. A. Oshorn. J. Am. Cheni. Six. 1976. 98. 2134: h) P. A. Weinheini. 1990; c) B. A. Arndtsen, R. G. Berginan, 7 A Nobley. T. H. Pe-
Chalonrr. M. '4. esleruelas, F. Joo. L. A. Oro. ~ / o n i o g i ~ n m uHyclrogiviafion,
.~ t e r ~ .4( ~ r.~ C, l i f w . Rids. 1995. 78, 154.
Kluwer. Dordrecht. 1994. Chap. 2 . [IOO] A first little piece is lound in R. Wesendrup. H. Schwarr. - 0 t ~ r i i ' .C/icmn. 1995,
[93] a ) L. S. Pu. A Y,nnamoto. S. Ikedo. J Ant. C h m . Siw. 1968, 90. 3896: h) A. 107. 2176. Aitgvii~.Cheiii. In[. E d EitgI. 1995. 34. 2033.
Misono. Y. Uchid;i, M. Hidai. T. Kuse, J. Clicvn. Soc. C h e r i i . C o tiinn~ ~1968. i . 981.