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This institution reserves the right to refuse to accept a copying order if, in its judgement, fulfillment of the order would involve violation of copyright law. No further reproduction and distribution of this copy is permitted by transmission or any other means.Rec'd: University of Arizona Interlibrary Loan : 2/18/2015 8:56:12 AM University of Arizona Library TBtOe Unverty td Tusson, AZ 85721 (620) 621-6434 / (520) 621-4619 (fan) "CLC: AZ Wot A Are. 150.135.45 158 LBRY-askaet@email anzona edu ILL #; 143226793 AINNICEN C Reference #: Journal Title: Photosensitization and photocatalysis using inorganic and organometallic compounds / Article Author: P. C. Ford, W. Boese, B. Lee, K. L. Macfarlane Article Title: Photocatalysis Involving Metal Carbonyls Volume: Issue: Month/Year: 1993 Pages: 359 - 390 (scan notes and ttelcopyright ‘pages for chapter requests) Email Address: ILL- Lending EMAIL ODYSSEY ENABLED Borrower: TXA. twa: 409976 ENNIO Call #: QD716.P45 P46 1993 Location: Science-Engineering Library IN LIBRARY Regular Shipping Address: ‘Texas A&M University - GWLA GWLA- SHIP WITH GREEN FLAG ‘GWLA- RETURN WITH ORANGE FLAG. Fax: (979) 458-2032 Notice: This material may be protected by Copyright Law (Title 17 U.S.C.). Paged by (MU (nitats)2 % Reason Not Filled (check one): 0 NOS 0 NFAC (GIVE REASON) 0 LACK VOLUMEnssUE i PAGES MISSING FROM VOLUME, ARIEL INFORMATION: Ariel Address: (nN Enter Arol Address Manually if unable to scan. If Ariel address lank, send via eral,PHOTOSENSITIZATION AND PHOTOCATALYSIS USING INORGANIC AND ORGANOMETALLIC COMPOUNDS Edited by K. KALYANASUNDARAM AND M. GRATZEL Institute of Physteal Chemistry, ‘Swiss Federal Institute of Technology, Lausanne, Switzerland na 5 KLUWER ACADEMIC PUBLISHERSP.C. FORD, W. BOESE, B, LEE and K. L. MACFARLANE PHOTOCATALYSIS INVOLVING METAL CARBONYLS 1. Introduction The focus of this chapter will be largely upon those photocatalyti involving simple mononuclear and polynuclear metal carbonyls of the general formula My(CO)x, although mixed ligand complexes which have at least several CO's in the coordination sphere of a single metal center will also be considered. ‘The photocatalysis described here is concerned not with nergy storage reactions but with processes which are isoergic or exoersic. The role of light in photocatalysis involving metal carbonyls is often simply to effect the dissociation of one or more ligands, usually CO, thus to open Coordination sites to other reactants and overcome the >30 keal mol! ‘ctivation energy needed to dissociate such ligands thermally. Ifthe resulting ‘umber of turnovers is small, the principal advantage would be to allow Access to a specific product not easily available by simple thermochemical routes with sufficient increase in value to justify the expense of utilizing light. If, on the other hand, photolysis transforms some precursor to an active species which survives numerous reaction turnovers, such a process Would be closer to being truly catalytic. En ag cat oil i alkene hydrogenation and hydrosilation (eq. 1) which are effected by a wide ‘varity of metal carbonyls under photochemical excitation. IY MCO REE CHE (E=H or R3Si) (1) Another important role of light in studying catalysis is the opportunity offered by the generation of reactive intermediates via high energy. but selective, pulse photolysis pathways. Characterizing the nature and reactivities of intermediates can provide important mechanistic insight not ‘only into photocatalytic processes but also into thermochemical catalytic ‘cycles. This chapter will also describe examples of such investigations. 39 RCH=CHy + E 1, Kalsenasundaron snd M. Grate feds Photorestization nd Phtrcaalat Lins Inorganic ant Organomet Composed, 89-390 81005 Rlaner Academic Pabison. Priced m the Neheronde360 POC. Ford etal In order to elucidate the mechanisms by which metal carbonyls may function as photocatalysts, one must first understand the fundamen! photochemical and photophysical properties of these systems. The mot comprehensive, although now dated, review of the photoproperties of met carbonyl complexes is the 1979 treatise by Geoffroy and Wrightoa [1 Some other reviews of a more specific nature are also listed (2-7). The present chapter will not attempt to be comprehensive but will present an overview of such properties for mononuclear and polynuclear met carbonyls then will describe some examples of the catalytic processes whist have been observed under photochemical conditions. Notably, tit photochemistry of the mononuclear complexes, especially those which a simple M(CO), species is dominated by CO labilization to give the “unsaturated” M(CO),.1 transients, which play the major roles it photocatalytic processes. There have been significant recent advances it characterizing the natures and reactivities of such intermediates, and thet studies will be summarized. The dinuclear and cluster carbonyls My(CO}x are dramatically different from the mononuclear analogs in the context‘ their spectroscopy and much of their photoreaction chemistry are dominatel by the metal-metal bonds. Thus, photoexcitation often leads tothe formation of odd electron (i.c., radieal) fragments via homolytic cleavage of ts bonds, especially in the case of dinuclear metal carbonyls. Such radicals generally display unusually high reactivities toward ligand substitution reactions and are more prone to undergo electron transfer processes Which ‘may have important consequences with regard to catalysis. For clusters of higher nuclearities, especially the trinuclear metal carbonyls, clus fragmentation must be considered, but as the nucleartics of the cluste increase, the relative importance of fragmentation versus ligand labilizaton diminishes. 2. General Photochemical Properties of Metal Carbonyls 2.1, SPECTROSCOPY ‘The absorption spectra (8] and luminescence spectra [9] of metal carbonyls have been reviewed and the intent of the present discussion is to provide @ brief overview of the spectral properties ofthis type of complex. Because of the relative high energies of the =* orbitals of the coordinated carbonyls, the lowest energy electronic transitions of the mononuclear carbonyls M(CO)y are generally ligand field (LF, ie.,d-d) in character. This is illustrated withPhotocatalysis Involving Metal Carbonyts 361 the spectrum of Cr(CO)g Figure 1a) which displays (10] two LF bands centered at 339 and 317 nm as expected for an octahedral low spin d® complex (although the covalency in the metal ligand bonding is reflected in the relatively high extinction coefficients). ‘The spectra ofthe heavier metal analogs Mo(CO)s and W(CO)s are quite similar as are those of such isoelectronic dS species as V(CO)g,, Mn(CO)¢* and Re(CO)g*. As one ‘might expect, singlet to triplet transitions are much more prominent in the absorption spectra of the heavier metal complexes. Metal to ligand (in this case CO) charge transfer (MLCT) 10 ost Absorbance ost 300 400 00 ‘Wavelength (am) Fig. 1 Spacwact some ypica!metalearbenyls. 2} CXCO}s: b) Mra(CO}19 and £) Rus(CO)32 i eytchexane sation,382 PC. Ford etal bands have been identified in the absorption spectra 2s wel, although thse occur at higher energies, e.g. 280 and 225 nm for Cr(CO)s. Thus, deste the relatively high field strength of the CO ligand, the expectation fo these complexes is that the photochemistry, which is generally dominated bythe lowest energy excited states (ES) will reflect in large part the ligand field ‘characters of those states. ‘Among other stable M(CO),, the absorption spectrum of the d carbonyl Fe(CO)s shows a lowest energy LF band as does that of the odd electron species V(CO),.[8]. However Ni(CO),, which is d10 and cannot show 64 transitions, displays a MLCT transition at 273 nm as the lowest energy bard in its absorption spectrum {11}. Absorption spectra become more complicated when other ligands L a introduced. Since L is generally weaker field than CO, LF bands a generally split and shifted to lower energy by replacing CO with L Furthermore, both MLCT and ligand to metal charge transfer bands might be expected depending upon the relative oxidizing or reducing ability ofthe ‘metal and of L, although because of the low valent nature of M in typical carbonyl complexes, LMCT bands appear to be rare. For example, the tungsten carbonyl complexes W(CO)sL, where L is an aromatic nitroge” heterocycle such as a substituted pyridine py-x, show both low energy spit allowed LF and MLCT bands in the absorption spectra (12. Whereas the Position of the LF band is relatively independent of the ligand L, especially, Of the substituent x for a series of py-x, the MLCT band energies are Very sensitive to the nature of x. Thus, by varying x, one can “tune” the ES tnergies as has been done with analogous coordination compounds of ruthenium (13) and of iron [14], For strongly electron withdrawing substituents, the MLCT bands of W(CO)spy-x are indeed the lowest enerzY absorptions. Investigations of the emission spectra confirm such behavior ‘and demonstrate that, while emission occurs from a lowest energy LF state for W(CO)spy, [12,15] strongly electron-withdrawing substituents like -CN lead to emission from a lowest energy MLCT ES [12,16]. Notably, MLCT ‘emission has also been observed for a variety of bidentate polypyridy! ligands (L-L) such as substituted bipyridines and phenanthvolines in complexes such as W(CO)s(L:L) and ReX(CO)3(L-L) 19]. ‘The most prominent features of the absorption spectra of metal-metal bonded dinuclear complexes such as the d-d7 dimer Mng(CO)j9 are the strong visible and/or near UV bands attributed to the x-o* and oP-o* transitions of the metal metal bond (1] (Figure 1b). A wide variety of other dinuclear complexes show similar spectral features, (8] and the resultingPhotocatalysis Involving Metal Carbonyts 363 ‘weekened metal-metal bonding character of the excited states has important connotations with regard to the photochemical reactivities of these dinuclear complexes. Luminescence has rarely been observed from such metal carbonyl dimers and apparently does not involve the M-M antibonding orbitals in the emitting state. For example, emission has been observed for the dinuclear compound Reg(CO)g(L-L) (where L-L is a 1,10- Phenantrlie), but the responsible ES hasbeen given a MLCT assignment 1. ‘The larger clusters such as the trinuclear iron triad carbonyls M3(CO)i2 QM = Fe, Ru, or Os) are often colored indicating low energy transitions Which are not present in the spectra of the M(CO)s mononuclear analogs. For example, the electronic spectrum of Ru3(CO)i2 (Figure 1c) is dominated by an intense absorption band (Emax = 7.7 x 103 M"l enrl) centered at 392 tim in cyclohexane solution (17].. This has been assigned qualitatively to 8 ° to o* transition between orbitals delocalized over the metal bonding framework [18]. Assignment of this transition as one between an orbital hich has a strong metal-metal bonding component ro one which is largely antibonding with respect 10 the same has been substantiated by X-c Calculations 19}. Higher energy bands have been tributed to excitation 10 2m ortital which has considerable antibonding character with respect 1 Be M.CO interaction [19]. Notably, the photochemistry of M3(CO)j2 follows a pattern consistent with these assignments. Excitation into the lowest energy Band gives cluster fragmentations while excitation at shorter wavelength ives CO photodissociation (20). Larger clusters also tend to be colored a the general assignments ofthese absorptions are to electronic transitions between orbitals of bonding and antibonding character delocalized over the ‘metal-metal bond framework [21]. Emission has been detected for several metal hydride carbonyl clusters, HsRes(CO)i2 and HgReq(CO)12” and assigned to such transitions (22). 2.2. PHOTOSUBSTITUTIONS OF MONONUCLEAR COMPLEXES Photochemistry has long been a synthesis tool of organometallic chemists ‘iven that electronic excitation can surmount enthalpy barriers which might otherwise require undesirably high temperatures, One such example is the ‘common synthetic route to tungsten pentacarbonyl derivatives W(CO)sL indicated by eqs. 2 and 3: W(CO + THF 'Y W(CO)sTHF + CO Q364 PC. Ford etal W(CO)sTHE + L > W(COsL + THF 8 ‘The labilization of CO is by far the most common photoreaction of simple ‘mononuclear metal carbonyls M(CO)x. This is not unexpected since LF excitation involves population of o* and depletion of xb MO's with respect to M-CO bonds. Furthermore, since M-CO bond energies fall into the range 30-40 kcal/mol [23], the energies of the near UV photons needed to excite the LF absorption bands generally are several times that required 10 dissociate CO. This is evidenced in metal carbonyl photolyses in the £28 ‘phase where not only are the products of a single CO dissociation observed, ‘but as photonic energies increase, products of multiple CO dissociation at also seen [2}. In solution and other condensed media, however, singe Photon events nearly always lead to labilization ofa single CO, independent of the photonic energy. In the presence of a trapping ligand L, quantum yields tend to be high, sometimes approaching unity. For mixed ligand complexes such as W(CO)sL, labilization of L is sometimes observed since the unique axis will usually have the weaker ligand field and ligand labilization generally will be along that axis, From a mechanistic perspective the most studied of the simple mononuclear carbonyls are the Group VI complexes Cr(CO)s, Mo(CO)s and W(CO)6, especially Cr(CO)g, Early investigations of these in low temperature matrices, especially by the Turner group [24], demonstrated that photolysis leads to dissociation of a single CO to give the M(CO)s transient which could be characterized by infrared and optical spectroscopy. Thes® studies also suggested thatthe unsaturated metal center could coordinate 10 matrix molecules, even a noble gas atom such as xenon. The potential role of solvent or other media molecules in coordinating such unsaturated centers ‘was further indicated by studies from Kelly [25], which demonstrated tht the transient formed from the conventional flash lamp photolysis of Cr(CO)s recombined with CO st a rate orders of magnitude slower in alkane solutions than in perfluoroalkane solutions. ‘These observations were explained in terms of the intermediate formed having a solvent coordinated in the sixth site, €.8.. CHCO}6 + SMS — CXCO)sS + CO ® CxCO)ss + CO Ze CHC + 8 ©Photocatalysis Involving Metal Carbonyls: 365 A series of very sophisticated laser flash photolysis studies have shown that the following sequence of steps is apparently occurring at least for ‘C(CO)s Firs, there is no measurable lifetime of the electronically excited Cx(CO)g, initial excitation is followed by CO dissociation to give a vibrationally hot Cr(CO)s fragment within 0.25 ps [26]. ‘This is followed by vibrational relaxation and solvent coordination within a few ps to give the C(CO)sS species with a solvent molecule bound to the metal in the vacant site (27). If the solvent is an alkane, this apparently coordinates with the electrons of a C-H bond donating to the metal in an “agostic” interaction, The actual formation of the solvento species appears to be quite non- Selective, When a solvent such as an alkyl alcohol or alkyl halide was used, the results of ps laser flash photolysis studies were interpreted in terms of an initially formed mixture of products including both alkane and oxygen or talide coordinated linkage isomers ofthe solvento product {28}. The alkane Coordinated species undergo isomerization to the more stable oxygen oF halide bound isomers in = 1 ns. How song are these solvent interactions with unsaturated fragments Such as Cr(CO)s? This question has been addressed by photoacoustica ‘alorimetrc measurements [29,30]. As expected, traditional Lewis bases Coordinate more strongly than do the alkanes bu the alkane chromium bond is a 10 kcal mol-!, ‘Time resolved IR spectral parently worth about 1 ‘ experiments have demonstrated an interaction of similar magnitude between W(CO)s and alkanes in the gas phase (31). Notably, even xenon has been shown in both solution [32] and gas phase {33] experiments to bind with 2 Cissociation energy of ~8 kcal mol"! ‘As noted above, one of the first indications that photogenerated "unsaturated" metal carbonyls such as Cr(CO)s were indeed solvent ‘coordinated was the demonstration in flash photolysis experiments thatthe rates of the back reactions with CO as well as reactions with other other ligands are markedly dependent on the nature of the solvent medium. For ‘example the second order rate constant ka for eq. 5 was reported to be 3.6 x 106 M-! s-} in cyclohexane[34} and 3 x 109 M7 sl in perfluoro- methyleyclohexane [25]. The reaction kinetics are second order, forthe large pan, the substitution mechanisms of these intermediates reacting with CO or other substrates are not yet fully elucidated. However, recent kinetics studies by Dobson and coworkers (35] ofthe reaction of CACO)sS with $= s-heptane or chlorobenzene with I-hexene or piperidine as a trapping agent have led to the conclusion that the substitution reactions occurred via competitive dissociative and interchange pathways. Complementary studies36 PC. Forde. using pressure effects to probe these mechanisms further concluded tht stronger nucleophiles tend to favor the interchange pathway, and that te interchange pathway take greater precedence as one descends the group VI complexes from Cx(CO)sS to W(CO)sS [36]. 2.3, PHOTOREACTIONS OF POLYNUCLEAR COMPLEXES Dinuclear carbonyls have two key features which differentiate them from mononuclear analogs. The first is the more obvious, ie., the presence of ‘metal metal bond and the role of the 2-* and G?-c* transitions which dominate the longer wavelength region of the spectra. For cases like Mna(CO)19 and Cp2W2(CO)g (Cp = 1-CsHs), which are linked by 2 single ‘MEM bond unsupported by bridging ligands, excitation into these bands can lead to homolytic scission of the metal-metal bond to give mononuclear fragments, such as 17-electron metal radicals (eq. 6) [5,7,37.38]- MxCO)x MY 2M(CO), © In analogy to the mononuclear carbonyls, higher energy excitation can led to CO dissociation to give “unsaturated” intermediates (eq. 7) [37391 MxCOrx Y — My(COp,1 + CO 0 However, the presence of ligands on the other metal center opens the possibility of these stabilizing the resulting reactive intermediate via som sort of bridging or semibridging interaction. Indeed there is evidence from ‘both low temperature experiments and time resolved infrared spectral stucies ‘that the Mng(CO)y intermediate produced by shorter wavelength photolysis ‘of Mn2(CO)i9 is not coordinated by alkane solvents but that the unsaturated metal center is stabilized by a semibridging interaction with a CO on the other Mn [40]. This tends to stabilize the intermediate toward reaction with other ligands or the back reaction with CO (kp = 1.2 x 108 M+ s'! in solution). A similar situation has been shown to be the case inthe photolysis ofthe iron dimer Cp2Feo(CO) . Flash photolysis experiments [2,41] with "time resolved IR detection” have shown that two intermediates are produced, CpFe(CO)z, the mononuclear radical product of homolytic bond scission, and the CO dissociation product CpFe(jt-CO)3FeCp, which has been stabilized by bridging ligands and is even several orders of magnitude less reactive toward ligands such as CO (kz = ~4.5x 10! Mt s+ jn cyclohexane solution) than is Mng(CO)s.Photocatalysis Inolving Metal Carbonyls 367 The 17 ¢« mononuclear metal radicals once formed have been shown to bedramatically more reactive toward ligand substitution reactions than 18.«. mononuclear complexes or their dinuclear precursors [42]. Indeed the formation of mononuclear radical intermediates can serve as catalysts for the Substitution chemistry of the dinuclear parents owing to the recombination of the radicals to give the substituted dimers [43]. After considerable ‘mechanistic investigation, it was concluded thatthe high radical reactivity can be attributed to facile associative reactions of the 17 e” species with the ‘nucleophiles to form 19 e* intermediates (eq. 8) [392,44]. Mn(CO)s + L == Mn(CO)sL == Mn(COxL + CO (8) ‘The 19 e° intermediates not only can undergo facile ligand dissociation to five a substituted 17 e° radical, but are also powerful reductants and can ‘ansfer an electron to other species in solution (e9.9) [6.45]. Mn(CO}sL + X SS= Mn(CO)sl* + X o .d observation some years ago (CO)i0, undergo heterolytic ionic products (€q. This redox pathway explains the unexpecte that certain dinuclear complexes, e... Maz a #leavage of the metal-metal bond in polar solvents to gi¥= 10) 13.6.46,47) Mnx(COjo + 38 by For clusters, metal-metal bonding becomes more delocalized 3 the huclearities increase. ‘This property, combined with the necessity breaking more than one M-M bond in order to effect fragmentation ¢9 ‘mononuclear products, suggests that this reaction should have a diminish efficiency for clusters relative to dinuclear complexes. This does indeed ‘appear to be the case in solution. While both metal-metal bond cleavage to give mononuclear fragments and ligand labilization play roles in the Photochemistry of trinuclear metal carbonyls, the quantum yields of cluster fragmentation (©) are modest [3]. For example in hydrocarbon solutions, 365 nin photolysis of Ru3(CO)12 in the presence of added ligands such as tsimethyl phosphite or CO leads to mononuclear products (eq. 11) with a limiting @r about 0.05 moles einstein" {20}. Mn(CO)s" + Ma(CO)3S3* (10) RuxCOn + 3L BY 3RuCOL ay368 PC. Ford et a While © proved to be relatively independent of the irradiation wavelength, the quantum yield for the competing photosubstitution pathway (®s,¢q. 12) proved to rise sharply with decreasing irradiation wavelength Ain-[48]. RufCO2 + L by RuxyCOyL + CO (12) Given the well documented role of homolytic M-M bond cleavage it photoreactions of dinuclear carbonyls, a logical hypothesis for the photofragmentations of trinuclear complexes would be to follow a similsr path to give a diradical. Indeed such an intermediate is attractive inthe context that the lower quantum yields could be attributed to rapid recombination of the radicals held together by the rest of the cluster. However, experiments with added chlorocarbons in Ru3(CO)12 photolysis solutions have shown that a trappable diradical is not an intermediate inthe photoreaction chemistry, but instead the intermediate formed is susceptible to trapping by two electron donors (ie., Lewis base nucleophiles) (ea: 13) 117,20,48-50). Rux(CO)i2 bY (Rux(CO);2) Hy Rus(CO)yaL #24, 3Ru(COML (3) ‘The presence of such intermediates was supported both by flash photolysis results in fluid solution [17,50] and by IR studies of low temperature glasses [51]. ‘This intermediate has been proposed to be an isomer ofthe starting cluster formed by heterolytic cleavage of a Ru-Ru bond and corresponding movement of a CO from a terminal to a bridging site maintain charge neutrality of both Ru centers [20,49] Similar Photofragmentation mechanisms have been proposed for the iron and ‘osmium trinuclear analogs {51-53}, and the photoreaction chemistry ofthese ‘winuclear carbonyls has been reviewed [3] Higher energy UV irradiation leads t0 predominantly to the ligand ‘substitution reactions with the quantum yield increasing with the excitation energy, although, photofragmentation continues to play a role at all Ri investigated. This reaction has been investigated in detail by conventional kinetic flash photolysis techniques [17], by low temperature frozen solution techniques (51) and by laser flash photolysis with time resolved IR detection [54]. ‘The photosubstitution pathway has been shown to proceed via CO dissociation to give the unsaturated cluster intermediate Rus(CO)t1, which reacts rapidly with ligands to form the substituted product or with CO t0 reform starting material (eq. 14). In alkane solutions, the back reaction of this intermediate with CO. (kz = 2.4.x 10? M-! sin isooctane solution) [54] is 3 orders of magnitude faster than that described above for either ofPhotocatalysis Involving Metal Carbonyl 369 the unsaturated intermediates Cr(CO)s or Mng(CO)p under similar conditions. This suggests that an alkane molecule is not coordinated to the 1nsaturated metal center, indeed the observation of a bridging CO in the low {temperature IR experiments (51} suggests that the intermediate formed is Stabilized by rearrangement of the coordinated ligands. One could envision the formation of a symmetrically bridged CO with a corresponding ‘movement of metal bonding electrons to give a Ru-Ru double bond to give metal centers with 18 e* counts (at least formally). Why the resulting intermediate is orders of magnitude more reactive than the Mng(CO)g analog remains to be explained. Rux(COr2 LQ ux(COpn) Hs Rug(COL (14) Tetranuclear clusters are even less prone undergo photofragmentation in solution. For example, when the hydride clusters HFeCo3(CO)12, HaFeRu3(CO)13 and HyRu4(CO)13 were photolyzed under CO in hydrocarbon solutions, fragmentations to smaller units were observed (¢-8-» £9.15), but quantum yields proved to be very low [55]- hy 1, + Ru(CO)s + ReyCO2 (15) HARudCO)s + CO Fe ags ver if In contrast, ligand substitutions (e-g., eq. 16) proved to be several orders o ‘magnitude more efficient at the wavelength utilized. an 0 (16) HARugCO)y3 + PPhy BY Gt am, H,Ru¢CO)PPbs + CO (16) Notably other tetranuclear clusters have been noted to undergo Photooxidation in halocarbon solutions owing to excitation into charge ttansfer to solvent transition (CTTS)(€q. 17) [56] hy G13 om) - (CO)]s [CpFe(CO)]¥’ ay) lepretcon CEB RaNGS Ice In a very broad brush set of generalities (3}, the polynuclear My(CO)x complexes undergo photofragmentation to smaller units with varying efficiencies at long wavelength excitation depending upon the nuclearity of the cluster. If the complex is dinuclear with an unsupported metal-metal ‘bond, the products ofthis reaction result from the initial formation of metal radical intermediates which may be very reactive toward ligand substitution310 PC Fordet al processes via associative reactions and toward electron transfer processes. ‘These may recombine to reform the initial dimer or substituted dimers or be trapped via redox processes to give mononuclear products. Photo- fragmentation with modest quantum yields is also seen for longer wavelength excitation of trinuclear clusters with the assistance of added ligands; however, the mechanism for this process does not appeat 1 involve the homolytic cleavage of metal-metal bonds (at least not for the systems subjected to close mechanistic analysis). Instead the operative mechanism {for cluster fragmentation appears to involve some type of associative attack of the ligand on photogenerated intermediates followed by fragmentation of the resulting species formed. Limited studies suggest that the efficiencies of fragmentation fall off dramatically for those clusters of higher nuclearites, although few examples have been investigated quantitatively. However, itis notable that, especially for excitation at shorter wavelengths, CO dissociation is a common and relatively efficient photochemical process for all metal carbonyl complexes. 3. Photocatalytic Activation of Dihydrogen Photocatalysis of alkene hydrogenation (e.g., eq. 18) has been noted fora ‘number of metal carbonyls including the mononuclear group VIII M(CO)s (M = Fe, Ru, Os) [4,57] and group VI M(CO)s (M = Cr, Mo, W) ‘complexes [58-60] as well as various clusters [61-63]. ‘The principal roles played by a metal catalyst in the hydrogenation of an unsaturated organic substrate are to activate the relatively inert H-H bond and to serve a8 # template where substrate and reductant can be united. Both of these require the opening of coordination sites in order for the catalyst to act on either the ‘substrate or reductant and catalysts are generally effective only under conditions where ligands are sufficiently labile to provide such access to the metal center. Photocatalysis of such reactions generally involves the labilization of one or more ligands which would not be prone to facile thermal substitutions under comparable, nonphotochemical conditions. Notably, both if both coordination of H (or its hydride equivalents) and the substrate are required, then labilization of more than one CO from 2 coordinatively saturated M(CO)y species is likely to be required. R-CH=CH-R' + Hy > RCH2CHOR’ as) “This can be illustrated with the photocatalytic hydrogenation of alkenes by Fe(CO)s, which is relatively nonselective and scts a8 a photocatalyst forPhotocatalysis Involving Metal Carbonsls an ‘he hydrogenation of linear or branched alkenes, eycloalkenes, dienes and sectylenes[$7]. Similar behavior has been noted for Ru(CO)s and Os(CO}s {57}. These mononuclear metal carbonyls also catalyze alkere hydrogenations thermally, but at much higher temperatures, presumably because of the high activation energies of thermal CO labilization (a Continuing theme ofthis chapter). For iron carbonyl, sequential photolabilization of two CO's is implicated bythe observation that photocatalyss i efficient even at -18° while thermal catalysis by the dihydride HoFe(CO), is very inefficient at this temperature 57}. Thus, a sequence of steps such as Scheme I has been suggested as the Catalytic mechanism. High quantum yields have been demonstrated for such Sequential CO substitution by (E-)eyclooctene for irradiation of Fe(CO)s Solutions in hexanes [64]. The Fe(n]2-olefin)(CO)3 complexes are extremely labile thermally as required for a likely participant in Dhotocalysis of akene hydrogenation or isomerization (ee below). Recent gas phase studies have demonstrated catalysis for eihene fT r——— “Fret Photolysis of a catalytically inert mixtures of Fe(CO)s. Ho Fe(Coys MSP FerConatkene) salkene bv | Fe(CO)s(alkene) AL Y FetCops(alkene) 7Fe{COn(atkene) i" \& HY 2 Fe(CO)s R ‘Scheme | Proposed mechanism for photocatalysis of alkene hydrogenation by iron ccbony!32 PC Forder al. (Quantum yields for ethene hydrogenation under these ambient temperature conditions exceeded 20. ‘The photolysis procedure generated a reservoir of Fe(CO)3(ethene)2 which is very labile and dissociates to give the active, unsaturated species Fe(CO)3(ethene). Added CO as well as photoliberated CO inhibits catalysis due to the back reaction to form the stable Fe(CO)a(ethene) [65]. Photocatalysis by M(CO)g (M = Cr, Mo, W) is much more specific than by the iron analog. Hydrogenation of conjugated dienes photocatalyzed by Cr(CO)¢ occurs only with those dienes which can assume a S-cis configuration and have coplanar double bonds. The result is 14H addition to these dienes (66]. Chromium carbonyl has very little activity for substrates such as terminal alkenes. Photocatalytic activities ofthe tungsten and molybdenum analogs are less than those for Cr(CO)g and tend to giv¢ ‘greater yields of isomerized alkenes. All three have been noted to be active in the photocatalytic hydrogenation of norbomadiene (NBD) to mixtures of norbornene (NBN) and nortricyclene (NTC) (eq. 19) [59,60]. An early mechanistic investigation proposed that the NTC product may be the result of CO photolabilization from the tetracarbonyl intermediate M(CO)a(n#-NBD) NBN NTC (itself formed by the photosubstitation reaction of M(CO)s plus NBD) 1° give a tricarbonyl complex which activates Hy for NBD reduction. The NBN product was correspondingly proposed to be the result of photodissociation of one of the alkene coordination sites of M(CO)s(n* NBD) to give a M(CO)s(H3)(q?-NBD) intermediate, which reacts further by transfer of the hydrogen to the remaining coordinated alkene to give NBN. ‘The ability of these group VI metals to coordinate Hz as M(CO)s(n?-H2) has been demonstrated by flash photolysis TRIR techniques in liquid xenon {67 in alkane solutions (68] and in the gas phase [69]. The binding is “nonclassical”, ie, coordination as He rather than as a dihydride, evidenced by the presence of a vu stretching band at about 3000 cm-1. Notably, reaction of Dz with Cr(CO)s(n2-H) in liquid Xe led to formation of Cr(CO)s(12-D2) but not of Cr(CO)s(n?-HD). In contrast the species Cr(CO}s(712-H2)2, which can also be formed in liquid Xe, reacts with D3 toPhotocatalyss Involving Metal Carbonyts 373 give -HD complexes, the H/D exchange presumably occurring upon formation of a Cr(CO)s(n?-H2)(n2-D2) species [68]. Thus coordination of ato Cr (and presumably to Mo or W as well) leads to the activation of the HH bond toward reaction with another coordinated ligand, in this case another dihydrogen, A reinvestigation of the M(CO)g/H/NBD system in ambient temperature ‘heptane using TRIR techniques was able to demonstrate the formation of the fac and mer isomers of M(ni’-NBD)(n2-Ha)(CO)3 and to determine the Feaction kinetics of these and related complexes [70]. This study concluded that transfer of Ha to NBD in the mer isomer is responsible for reduction to NBN, while the analogous process in the fac isomer leads to formation of NIC (Scheme 11). Notably, fac and mer isomers of M(y*-NBD)(n?- schanisms far photocatalysis of nosbornadiene Scheme 1 Proposes mechs tor ot hydrogenation bythe group Vicarbonyls M(CO}Gasc 374 PC. Fordet al. NBD)(CO)3 were also formed, indeed under the catalytic conditions tes were likely to be the predominant trisubstituted complexes. preset. Photochemically induced fac to mer isomerization of these species my account for the predominance of NBN as the photocatalytic hydrogenation product when M = Mo or W. It is notable that again the only role of th light suggested in these photocatalytic processes is to effect liga labilization. This point was dramatically illustrated by the recent isolation and characterization of the thermally labile complex mer-Cx(CO)3(1* NBD)(n?-cthene) by Grevels and coworkers [71a]. When this species ws used as a catalyst for NBD hydrogenation in the dark, the produt NBNINTC distribution 1/3.2 was nearly the same as that obtained in the photoinduced catalysis with Cr(CO)4(n4-NBD), thus the photolytc detachment from the later complex and the loss of ethene from mer Cx(CO)3(n#-NBD)(n2-ethene) generate the same catalyst system. Another tricarbonyl species Cr(CO)3(n®-1,3,5-cycloheptatriene) has beet shown to serve as a photocatalyst for 1,6 Hz addition to cycloheptatrent (71b]. The suggested mechanism involved a photoinduced 11° 01?" hapticity change of the coordinated cycloheptatriene allowing access of H2™ the vacated coordination site. 4. Photocatalytic Hydrosilation and Isomerization of Alkents Hydrosilation of alkenes has been shown to be photocatalyzed with a varie of mononuclear and polynuclear carbonyls under mild experimental conditions. [67,72-75]. For photocatalysis by Fe(CO)s and Cr(CO)s a8 their homologs, mechanisms analogous to those described for hydrogenations are apparently responsible [76]. With Cr(CO)g only 1,3 dienes are reactive and photocatalysis leads to 1,4-hydrosilation [67]. ‘major difference, however, is that the bulky silane imposes certain ster constraints on the reactions, thus hindered dienes which can be hydrogenated do not undergo hydrosilation. Furthermore, silation of unsymmetrical dienes occurs at the less hindered terminal carbon. Although ‘oxidative addition of silanes to unsaturated metal centers generated by ligand ‘photodissociation is certainly observed [76,7}, "nonclassical" or 3-center bonding of Si-H to species such as Cr(CO)s has also been concluded [78] Notably the bonding of Si-H to such centers is about twice as strong as the corresponding complexes with alkanes. ‘With Fe(CO)s, photohydrosilation of alkenes is less selective and also gives a mixture of products including substantial fractions of alkanes andPhotacatalsis Insolving Metal Carbonyts 315 alkenyl silanes [72,73]. This observation suggests that once an iron esi alkyl intermediate is formed along the pathway to hydrosilation, pane side reaction ofthis species would be B-hydride elimination to give a silyl alkene plus dihydrido iron which can hydrogenate another alkene. This reaction mode has been demonstrated in photolysis studies of ethene Saturated alkane solutions of Cp*Fe(CO)2SiMe3 (Cp* = 75-MesCs). Photolysis liberates CO (with quantum yield of 0.2) followed by addition of ethene to give Cp*Fe(CO)(C2H,)SiMe3. The ethene reversibly inserts into the Fe-Si bond to give a B-silyl ethyl intermediate which in the absence of Lewis bases undergoes -hydride elimination to give Cp*Fe(CO)2H plus ‘Me3SiCH=CHp [73]. ‘The substituted iron carbonyls Fe(CO)4PPh3 and Fe(CO)3(PPh3)2 have also been examined as photocatalysts for hydrosilation; however, the Qualitative reactivity features were found to be similar to those of Fe(CO)s, (74). In addition the polymer anchored derivatives Fe(CO)4(PPh2-poly) sand Fe(Co)s(PPho-poly)2 (where PPh poly is the polystyrene bound dipheny! Phosphine) proved to be effective photocatalysts for both hydrosilaion and hydrogenation [74]. Photocatalysis of alkene hydrosilation is also effec. by metal carbonyl clusters [61]. ean Photolysis: of dinuclear complexes such as Con(CO)s and pas rs in principle fad to 17 electron metal radicals which ean participate in further catalysis with silanes. Such species might be anticipated fo act in one wo ways Abstraction ofa hyrogen from a-Si bond in 2 manser Which might favor radical chain reaction catalysis of hydrosiaton And might be attractive given the lower homolytic dissociation energy of Si-I bonds (relative to H-H). Alternatively, the highly labile 17 & species Provide routes for active substitution of alkene substrates and or silanes into the coordination sphere. In this content, itis notable that while solutions of I-pentene and ‘Cox(CO)g proved fo be essentially unreactive when irradiated, solutions of Coa{CO)s, I-pentene and HSiEts were active for pentene isomerization with small concentrations of silylalkenes also found as an end product {75}, However, achain reaction appears unlikely for the hydrosilation pathway; the apparent fate of the cobalt radicals is to form 18 e- species such as HCo0(CO)s and ErsSiCo(CO)s which themselves are photo or thermal catalysts for pentene isomerizations. The silyl alkene products appear 10 result from the formation of E1;SiCo(CO);(1-pentene) followed by insertion of pentene into the Si-Co bond, then -hydride elimination.316 PC. Forde al Photocatalysis of alkene isomerizations and related processes has aso been noted for a number of other common carbonyls including Fe(CO}s, Fe(CO)sPPh3, Mo(CO)e, W(CO)s, Ru(CO)sPPh3 and Rux(COh2 {61,74,79-82]. In some cases quantum yields substantially in excess of unity have been reported consistent with the photolytic formation of 3 catalytically active species capable of numerous turnovers. The photocatalysis of 1-pentene hydrogenation by Fe(CO)s is accompanied by isomerization of the substrate to 2-pentene [57]. Such a pathway coald ‘occur via a B-hydride elimination pathway comparable to the reverse of SEP 2 in Scheme I, but a more likely pathway would be via a C-H insertion reaction of the intermediate Fe(CO);(alkene) to give an alkyl hydride intermediate as in eq. 20. (CO);Fe— || a ‘Transfer of the hydrogen back to the organic fragment but to the terminal carbon would give 2-pentene (eq, 21) H (CONFER (COyFe— | @ yo , ‘That such a mechanism is operating was confirmed by using Dz rather that Ha, In this case photocatalysis at 25° gave dideuterio pentanes plus now deuterated 2-pentene [57]. However, at lower T, both mono- and not deuterio pentanes as well as mono-deuterio pentenes were found to be products under photocatalysis conditions. These observations would be ‘most consistent with step 4 of the scheme having a sufficiently highet activation energy than the summed reverse reactions, so that H/D scrambling becomes competitive with alkene hydrogenation. The probable role of tricarbonyl complexes, e.g., Fe(CO)3(alkene)2, it these isomerization cycles has been demonstrated by preparing these species photolytically from Fe(CO)s [66,79], Both Fe(CO)3(alkene)2 (and Ru(CO)s(alkene)2) proved active thermal catalysts for the isomerization of 1-pentene at 293 K. However, a competing dehydrogenation process which leads to the formation of stable and catalytically inactive (at 298 K) M(CO)3(n*-1,3-pentadiene) complexes serves to deactivate thesePhotocatalyss Involving Metal Carbon on systems {66]. Photochemical techniques have also been us ene isomerization catalyst rom Fe(CO}sphyssoted ino prone en alas (82]. Again it appears that the principal species responsible trcarbonyl, Fe(CO)3(alkene)p(abs). ‘Another photocatalytic reaction of some interest is the cyclic dimerization of alkenes, which has been reported for a number of different metal carbonyls including Fe(CO)s, Cr(CO)g, Ni(CO) and several substituted analogs [83-85]. Although such dimerizations are catalyzed thermally by Some of the same species, the stereochemistries of the products differ depending both upon which complex is utilized and whether the reaction is caried out thermally or photochemically. The dimerization of butadiene to 4-vinyleyclohexene photocatalyzed by the iron dicarbonyl Fe(CO)3(NO)2 fas been studied by examining the intermediates formed when the photolysis vas carried out in lig. Xe [85]. The key species was found to be the disubstituted species Fe(NO)2(n]2-butadienc)2 which was proposed 10 Undergo isomerization to Fe(NO)x(n*-butadiene}(n?-butadiene) which can ‘undergo an internal Diels-Alder cyclization to the vinyl eee Ties Another interesting photocatalytic process ae ing 1) i cael 2Uditon ofthe eyelic teuafluorodisilane 0 eyelohexadiene [86 TEN this occurs at 100° Cao give the riyele product oF 18 Aut Photocatalysis at ambient temperature with Fe(CO)s & Product of 1,2 addition.(eq. 22) r/R ca Tr: O § ‘SiF; ‘y 2 ~\ Sh_UR hy, Fe(COs cx Fy 2 Stoichiometric photoinduced {6+2] cycloaddition of an alkyne to the organic ligand of Cr(CO)3(n6-1,3,5-cycloheptatriene) has also been reported (ib.378 P.C. Ford erat 5. Photocatalytic Carbonylations The carbonylation of hydrocarbons serves as an important catalytic methodology both for extending the carbon backbones of organic compounds and for adding oxygen functional groups such as alcohols, aldehydes or carboxylic acids. Hydroformylation of alkenes (eq. 23) is ‘carried out in various thermal catalysis schemes [87] and photocatalytic ‘examples have been described (see below) [88,89]. R-CH=CH2 + CO + Hg > RCH2CH2CHO /RCH(CHO)CH3 (23) Photocatalytic activation of C-H bonds of alkanes and aromatic hydrocarbons including photocatalytic carbonylation (4,90-94) has received Considerable attention in recent years, although the more extensively studied systems have been those based on cyclopentadienyl or phosp complexes, especially those of rhodium and iridium. Described in this section are the more limited examples of photocatalytic carbonylation based ‘on metal carbonyls, For example, photolysis (Pyrex filter Hg/Xe lamp) of several ruthenium carbonyls (Ru(CO)3L2, Ru(CO)4L. or Rux(CO)y2, L = PPh) in benzene was shown to promote hydroformylation of ethene and of propene under Temarkably mild conditions (0.7 atm of 1/1 CO/H at ambient T) [88]. For ‘comparison, the same ruthenium carbonyls catalyze such hydroformylations thermally but require much higher CO/Hg pressures (> 70 atm) and temperatures (120-1500) [87]. As noted above, these ruthenium complexes are also effective photocatalysts for alkene hydrogenation as well as of the Product aldehyde. Therefore, the ethene hydrogenation photocatalyzed by Ru(CO):PPh3 gives ethane, propionaldehyde and I-propanol as products with hydrogenation proving to be about twice as facile as hydroformylation and the aldehyde/alcohol ratio decreasing throughout the reaction reflecting the sequential formation of the products. As many as nine turnovers were observed. With propene, hydrogenation was favored over hydroformylation products in 4/1 ratio but the more desired straight chain hydroformylation- Iaydroxymethylation products were favored over the branched chain ones by 39/1 ratio. Again, the key photochemical step is to labilize CO. The resulting unsaturated ruthenium intermediates are then able to participate in the thermal reactions proposed in Scheme IILPhotocatalssis Involving Metal Carbonyls 319 Ru(CO),L | feo oy Ru(CO),L #2» H,Ru(CO)sL co K FH wz Pu(CO)aL Roy ‘0 ee pPUCOML OO HAulZ(CO)aL (L=PPh 5,Z= akene) Scheme ill Proposed cyclo for photocatalysis of ethene hydroformylation by UCOMPPr Photocatalysis of benzene carbonylation (eq. 24) has been reported for the complexes Ru(CO)3¢PPh3)2 and Ru(CO)sPPh3 in benzene under CO (500.800 tor) using a pyrex filtered 200 W Hg/Xe lamp [96]. ust» PhCHO ea parently Timited by the cal mot!) and back was demonstrated by PhH + ©O The amount of benzaldehyde formed is small and ap unfavorable thermodynamics (AG298 = + 1.7 ke decartonylation of benzaldehyde. The reversibi ‘fecting the photolytic exchange of !3CO into benzaldehyde. ; ‘The disubstituted complex is converted by photolysis under the reaction Conditions to Ru(CO)sPPh and this appears 0 be the precursor for the Photocatalytic process. ‘The unsubstituted cluster Rug(CO)12 proved be ineffective as a photocatalyst for ethene hydroformylation, although under the photolysis conditions the cluster should fragment to the unsubstituted ‘mononuclear species Ru(CO)s (171. Twas proposed that the key photochemical step is CO dissociation from Ru(CO)gPPhs to give the intermediate Ru(CO)3PPh3 which is capable of activating benzene by oxidative addition to a C-H bond (Scheme IV). Notably, the photocataly increased with increasing Pco- Thus, interception of the unsaturated tricarbonyl intermediate by CO is less important than other considerations. It was not clear from these studies380 PC Ford etal Ru(COydL 2} feo “ye Ru(CO}st. H, \ Pucoys. (PrH)RU(CO}L ney ‘0 \ 460 HY AUCOjst. Pw \iA (L= PPh) Scheme 1V Proposed cy u(COy,PP hg for benzene carbonylatian photocatalyzed YY “whether the effect of increasing Peg was not merely a reflection of mass action effects, PRN Sh ‘Attempts were made to overcome the thermodynamic limitations PY hhydrogenating the benzaldehyde product as it was formed. Both Ru(CO)sPPhg and Ru(CO)3(PPh3)2 were found to act as photocatalyst fr the hydrogenation of benzaldehyde to benzyl alcohol under 400-600 tom Ha Furthermore, the presence of Hz apparently suppressed the decarbonylation of benzaldehyde. Nonetheless, although benzyl alcohol was indeed formed when the photolysis of benzene solutions of Ru(CO)sPPh3 end Ru(CO)3(PPh)2 were carried out under a mixture of CO (225 tort) and H2 (225 ton), the product yields were not significantly higher than when the photolyses were carried out analogously but only under CO. Increasing the HCO ratio also had litle effect on the reaction efficiency. In this context these results appear to contradict the conclusion that the low efficiencies of benzene carbonylation are the result of thermodynamic limitations, since the hy¢rogenation to benzyl alcohol should serve to shift the equilibrium and increase benzene functionalization. Further investigations of this interesting system are warranted. Equation 25 illustrates another photocatalytic carbonylation (97] which has been demonstrated for the mononuclear carbonyl Pt(CO)aL2 (L = AsPhs or PPh) and the polynuclear species Mng(CO)10, Co2(CO)g, Fe3(CO)y2.Photocatalsistnvoling Metal Carbonsls 38 Rux(CO)jg and 033(CO))2. I proved ineffective. 1" COMTRSt the Broup VI carbonyls M(CO), RI + CO(I am) + CHOH GLC RCOOCH; (25) {tis not clear what role is played by the KyCO3 base. ‘The reactions were carried out in methanol solution, and it has Previously been demonstrated that certain of the above carbonyls react rapidly with methoxide to form methoxycarbonyl adducts [98]. It is likely that such adducts play a significant role in the photocarbonylation processes. A somewhat similar photocatalytic reaction (eq. 26) has been reported for the carboxylation of aryl and vinyl halides under phase transfer ArX + CO + 20H —2Y350.nm)CONCOs CeHig(aq. NaOH), BusN*Bs ArcOy +X'+H20 26) olution Conditions [99] (alkaline aqueous solution in contact with benzene sé of the alkyl halide), In this case Cop(CO)g was used as the photocatalyst Precursor. 6. Other Photocatalytic Processes 6.1 THE WATER GAS SHIFT wn to be The water gas shift reaction (eq. 27, WGSR) has been shown 10 ees en a at 2 en lng te nd Acidic solutions depending on the specifies of the systems [100,101]. The WGSR serves as a key step in any scheme for the utilization of coal and other carbon sources for liquid fuel or chemical production. Furthermore, the reverse of the shift reaction serves aS a model for one pathway to COz activation (102). HO + Photochemical activation of the WGSR has also been claimed in several cases. For example, white light photolysis of aqueous THF or DMF solution of HFe(CO}s" under CO sat 25° generates Hy plus CO in the correct stoichiometric ratio with fttle decomposition of the iron complex {103}. co = ht CY en382 PC Ford eral tv HFe(CO)," —~\ HFe(CO)," oI HFe(CO)q" COz HFe(CO)7? HFe(CO), oF or He HO 2c0 Fe(CO), + Fe(CO)2 ~~ Fe,(C0)* ‘SchomeV Cycle for photocatalytic water gas shit reaction catalyzed by Fo(COls: ‘Tumover frequencies Ti(Ho) of about 2 per day were recorded under the photolysis conditions. ‘The thermal catalysis by alkaline aqueous methanol solutions of Fe(CO)s has about the same activity at 100°, The photochemical step is involved in the generation of dihydrogen from HFe(CO)4", one of the rate limiting processes in the thermal catalysis [100]. ‘The cycle described in ‘Scheme V was proposed as the photocatalytic mechanism. Quantum yields for Hz formation from HFe(CO)," in 9/1 THE/H20 were determined to be 0.08 at hire 366 nm and 0.14 at 313 nm under either a AT oF CO atmosphere. If one assumes the validity of the scheme, the insensitivity of photochemical Hp production toward the presence of CO must lead to the conclusion that the reactivity of HFe(CO)," withthe photolysis intermediate HFe(CO)s" is a least comparable to that of CO (The concentration ratio [Fe(CO}s VCO} is about 10/1 under the conditions ofthe experiment.) The scheme also requires that conversion of Fe(CO)s to the hydride anion HFe(CO)¢" be rapid relative to photochemical Hg production. Consistent ‘with this is the very large second order rate constant for the thermal reaction cof Fe(CO)s with hydroxide in solvent mixtures and conditions comparable to those used for the photoreaction (104]. Interestingly, the proposed bimolecular pathway for Hz formation described in the photochemical scheme has not received serious consideration in discussions of thermal WGSR catalysis by Fe(CO)s.Photocatalsis Involving Metal Carbonyts 383 Another WGSR system subjected to photochemical activation based on M(CO}g (M = Cr of W) in alkaline solution, Tekan ‘teen weed that, under certain conditions (T > 1300), the WGSR eycle of the thermal catalysis by such Solutions involves the uncatalyzed reaction of CO plus OH togive HCOy: followed by the metal catalyzed decomposition ofthe formate 10 He plus CO2{100,105}. For the latter reaction the large AH? value (435 kcal mot!) was interpreted to indicate rate limiting CO dissociation from M(CO)s. Grant and coworkers have demonstrated that pulsed laser ion (337 nm) of M(CO)s in alkaline H20/MeOH solution of NalHCO3} tead to photocatalyzed formate decomposition under mild conditions (5-659) [106]. Once initiated by irradiation, the catalysis continues indefinitely in the dark unless CO is added. This result suggests that the role of photolysis is to labilize one or more CO's to give solvated Species capable of catalyzing the formate decomposition at much lower temperatures than required for the thermal WGSR. Notably, while this study demonstrated the viability of the WGSR catalysis by the previously Proposed mechanism, it does not directly represent a water gas shift Photocatalyst, since the production of HCO" from OH" plus CO is quite Sow under the conditions studied 1100, supported catalyst for the WGSR has been prepare a blag carbonyl clusters [Piy(CO)el (2 = 3) in the pores sas Zeolites [107] which is active forthe water gas shift and its reverse over temperature range (300-423 K). The WGSR activity was dramavically enhanced by factors as large as 38 by white light illumination, Tt was speculated that the rate enhancement can be attributed to photoinduced cleavage of water (by oxidative addition to the supported metal clusters) and subsequent reactions of the resulting absorbed OH and H equivalents with CO to give CO> plus Hz. wrepared by intercalation of 6.2 PHOTOCATALYZED POLYMERIZATION OF ALKYNES Alkyne polymerizations photocatalyzed by metal carbonyls have been reported by several groups [108,109]. For example, Geoffroy and coworkers have demonstrated that photolysis of W(CO)¢ in the presence of Phenylacetylene or acetylene leads to large yields of poly(phenylacetylene) and trans polyacetylene. With acetylene, light was only required to initiate the polymerization which continued unabated after irradiation was stopped. However, the reaction with phenylacetylene required constant photolysis. It ‘was suggested that the photoreaction involved CO dissociation to give a7]? alkyne complex which undergoes rearrangement of the coordinated terminal384 PLC. Ford etal alkyne to give a vinylidene intermediate (eq, 28). Similar vinylidene species prepared synthetically have been shown to be thermal catalysts for such polymerizations. Presumably, this species is labile towards loss of CO 10 give a n/-vinylidine 1?-alkyne complex which undergoes cyclization to a cyclometallobutene to form carbon-carbon bonds. hy W(CO)s + RC=CH CO W(CO)s(7?-RC=CH) » — W(CO)s(C=CHR) (28) Others have reported analogous photocatalyzed polymerizations when ‘W(CO) js irradiated in halocarbon solvents in the presence of alkynes and halocarbene complexes have been suggested as the key intermadiates (110). Hialocarbene intermediates have also been implicated in the photocatalysis of olefin metathesis reactions by the group VI carbonyls M(CO)s in carbon tetrachloride [111,112]. 7. Summary ‘The material reviewed above indicates that metal carbonyls indeed can act 88 photocatalysts in transformations of various substrates, including alkene hydrogenation, hydrosilation, hydroformylation and metathesis, aromatic hydrocarbon cazbonylation, alkyne polymerization and the water gas shift. ‘The photochemical role for most of these processes seems to be the simple labilization of CO from the metal in order to generate vacancies in the coordination sphere. Given that thermal CO dissociation from coordinatively saturated metal carbonyls of the type Mx(CO)y generally requires activation energies exceeding 30 kcal mol"! the photochemical method allows the preparation of these transient species at ambient temperatures. The potential benefit of such photocatalysts would be the ‘opportunity to cary out the appropriate chemical transformations on systems ‘in which either the substrates or the products may be sensitive to elevated temperatures. The disadvantage of this type of catalytic system is that the CO liberated in the photochemical step often competes with the reaction substrates for the metal sites so that constant irradiation is necessary to sustain the catalytic activity. In this context, itis likely that interesting new photocatalytic transformations may be discovered for dinuclear metal ‘carbonyls for which the photochemical reactions produce metal radicals possibly capable of catalytically important redox processes. PhotochemicalPhotocatalysis Involving Metal Carbonyts 385 techniques, especially flash photolysis experiments with time resolved infared spectral detection of transient species, also provide an entry into the investigation of the structures and reaction dynamics of the reactive ‘rganometallic intermediates which have relevance to understanding the mechanisms of both thermal and photochemically stimulated catalysis jvolving various metal carbonyls (113). 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