Tetrahedron 60 (2004) 71177140

Olen metathesis
Robert H. Grubbs*
The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA
Received 10 May 2004; accepted 11 May 2004

AbstractOlen metathesis has become a tool for synthetic organic and polymer chemists. Well-dened, functional group tolerant catalysts have allowed these advances. A discussion of the evolution of mechanistic understanding and early catalyst developments is followed by a description of recent advances in ruthenium based olen metathesis catalysts. Catalysts improvements have led to new applications in ring closing metathesis, cross metathesis and materials synthesis. q 2004 Published by Elsevier Ltd.

As with most catalytic processes, olen metathesis was found by accident. It was discovered as an outgrowth of the study of Ziegler polymerizations with alternate metal systems.1 By the late 60s, the Phillips group developed a commercial processthe triolen processand made the scientic community aware of this unique reaction.2 My introduction to olen metathesis occurred during a group meeting while I was a postdoctoral fellow in Jim Collmans group at Stanford. It became obvious at that meeting that the mechanism of the metathesis reaction would require new intermediates and mechanic pathways unlike any known at the time. In addition to the intellectual challenge, understanding the mechanism would allow for the development of better catalysts.3 The initially proposed mechanism was that of a pair-wise exchange of alkylidenes through a quasicyclobutane mechanism in which two olens coordinated to the metal and exchanged alkylidene groups through a symmetrical intermediate. With a few assumptions, this mechanism could account for most of the basic metathesis transformations.4 In addition, other mechanisms5 were proposed for the isomerization of metal diolen complexes including metallacyclopentane rearrangements (Scheme 1).6

Chauvin proposed a new mechanism to explain a surprising set of observations.7 He observed that in some cases where a pair-wise mechanism such as the quasicyclobutane mechanism, predicted only the two olens resulting from pair-wise exchange of the two ends of the stating olens, the olens resulting from cross products were observed very early in the reaction. Although some assumptions would allow the pair-wise mechanism to account for this result, Chauvin proposed a mechanism that involved the fragmentation of the olen (a non-pairwise mechanism) through what has become known as the carbene mechanism (Scheme 2).

Scheme 2.

Scheme 1. Keywords: Olen metathesis; Polymerization; Carbene. * Tel.: 1-626-395-6003; fax: 1-626-564-9297; e-mail address: [email protected] 00404020/$ - see front matter q 2004 Published by Elsevier Ltd. doi:10.1016/j.tet.2004.05.124

Independent of the metathesis mechanism research, considerable progress was being made in the development of metal carbene (alkylidene) complexes. Work by Casey that demonstrated a metathesis like exchange between a Fischer carbene and an electron rich olen8 and the demonstration by Schrock9 that metal alkylidenes could be formed under metathesis like conditions made this mechanism even more appealing. Katz, in experiments similar to that of Chauvin, dened the basic assumptions and further strengthened the arguments against the pair-wise mechanism. He demonstrated that the cross-over products were formed even at zero time.10 On returning from a meeting in December 1974, where I had discussed the mechanism of metathesis with Chuck Casey, a mechanistic study involving a ring closing metathesis

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reaction with deuterium labeling was designed which would allow a distinction to be drawn between pair-wise and nonpairwise mechanisms. With in a couple of months, 1,1,8,8tetradeutero-1,7-octadiene had been prepared and mixed with the non-deuterated analog and allowed to undergo metathesis with catalysts known at the time to produce cyclohexene (not reactive in metathesis) and deuterated ethylenes. Since unreactive cyclohexene is formed, the system allows the fate of the ends of the olens to be precisely dened and the expected product mixtures to be calculated for pair-wise or non-pairwise exchange of the terminal methylene groups. The statistical mixture of labeled ethylenes (1:2:1 ratio starting with a 1:1-mixture of D4:D0-1,7-octadiene) was formed as the kinetic products instead of the ratio of 1:1.6:1 calculated for a pair-wise mechanism.11 To explain this experiment by the pair-wise mechanism required unreasonable assumptions (Scheme 3).

Although some catalysts with activity limited to strained olen polymerization were prepared from late metal precursors,15 the most active catalysts were prepared by the alkylation of high oxidation state early metal halides. The rst high oxidation state alkylidene complexes of Schrock did not induce olen metathesis.16 The Fischer carbenes, which are low oxidation state carbenes, were shown to be olen metathesis catalysts of low activity.17 Although fragments of the initiation carbene were later observed as end groups on the polymers produced by such catalysts, the intermediates in the reaction could not be observed.18,19 The high oxidation state, late metal complexes of Tebbe,20 Schrock21 and Osborn22 provided the transition to the synthesis of well-dened catalysts. In contrast to classical catalysts, well-dened catalysts are those were the propagating species can be observed and controlled. Such systems represent the transition to modern metathesis catalysis. Fred Tebbe demonstrated that a titanium methylene complex would catalyze the non-productive metathesis exchange of the methylenes between two terminal olens. Although the catalyst was not particularly active, it served as an excellent model system since the complex was very stable and the propagating methylidene could be observed and studied.23 We developed two areas of work based on the Tebbe observations. With Dave Evans, we initiated an investigation of this complex, now know as the Tebbe Reagent, in a Wittig type reaction for the conversion of esters to vinyl ethers (Scheme 4).24

Scheme 3.

Katz reported a similar ring closing experiment in which phenanthrene was the ring closed product. He carried out a precise analysis of the isotope effect and an alternate analysis of the expected mechanism for the pair-wise mechanism.12 The key feature of these experiments was the determination that the observed products were not scrambled in a secondary reaction. Although these experiments strongly supported the non-pairwise mechanism, the experiments that demonstrated that the initial products observed did not arise from a secondary scrambling mechanism required several assumptions. I was not totally convinced until, we completed one of my favorite (but probably least read) mechanistic studies using cis, cis1,1,1,10,10,10-hexadeutero-2,8-decadiene in place of labeled 1,7-octadiene. In this experiment, the labeled product was cyclohexene and cis and trans 2-butene. By coupling an isotopic label with a stereochemical label, we could demonstrate that the unfavored cis isomer of the product 2-butene was completely scrambled as required for non-pairwise mechanisms.13 Katz presented a complete analysis of the Chauvin type of experiment and demonstrated that the ratios of observed products were inconsistent with a pair-wise mechanism.14 Although these experiments did not prove the Chauvin mechanism, the approach of using ring closing reactions to produce 6-membered rings and labeled acyclic olens nally discredited the pair-wise mechanism and most researchers quickly considered variations of the basic Chauvin mechanism as the most reasonable.

Scheme 4.

A second project involved the synthesis of unsymmetrical Tebbe complexes for use in a mechanistic study to determine the structure of the metallacycle intermediate. Much to our surprise, when Tom Howard added pyridine to the reaction, a metallacycle (2) was formed as a stable complex whose structure was determined.25 A number of detailed studies demonstrated that this metallacycle was a competent intermediate for the Tebbe metathesis mechanism (Scheme 5).26 These experiments established the metallacyclobutane as a viable intermediate in olen metathesis. Osborn and Ivin found a catalyst system that showed both the propagating carbene and the metallacycle.27 Schrock28 and later Basset29 developed early metal complexes that were single component and showed useful levels of activity. However, the break through came with the Schrock groups development of tungsten and molybdenum alkylidene complexes that

Scheme 5.

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contained bulky imido ligands.30 These complexes showed high activity, could be prepared on moderate scales and were sufciently stable to study in detail. These catalysts provided the rst efcient and controlled catalysts for metathesis and were the basis for our initial work in organic and controlled polymer synthesis.31 For example, the high activity of the tungsten-based systems allowed for the polymerization of cyclooctatetraene to polyacetylene32 and benzvalene to polybenzvalene,33 work that opened our continuing studies of conjugated polymers. In a continuation of the Tebbe mechanistic studies, Laura Gilliom found that the Tebbe complex would form a stable metallacycle with norbornene.34 When this complex was heated with more norbornene, a polymer was formed. The polydispersity of the resulting polymer was unusually narrow. Further studies demonstrated that reactions, which utilized these complexes, would polymerize norbornene at higher temperature but would be inactive for polymerization when cooled to room temperature. The resulting polymer contained an active titanacyclobutane at the end of the polymer that could be reactivated on heating. The polydispersity could be further narrowed by the design of a metallacyclic initiator based on diphenylcyclopropene35 that was more reactive than the propagating species (Scheme 6).36 It has become apparent that most stable well-dened initiators of metathesis give living polymerizations with norbornenes. In many cases, techniques must be developed to produce favorable initiation/propagation rates to produce narrow dispersity polymers. To fully exploit the polymer chemistry of the well-dened metathesis catalysts, part of my group turned almost full time to the study of polymer chemistry and a course in polymer chemistry was initiated at Caltech. Wilhelm Risse

and Lou Cannizzo developed a variety of techniques for the precise synthesis of low dispersity block and star polymers.37 Most of the techniques, which are now use with better catalysts were developed during these studies. John Stille combined the olen metathesis activity of the Tebbe reagent with its Wittig nature to produce a key intermediate ( 5 ) for the synthesis of Capnellene (Scheme 7).38 The availability of well-dened catalysts from the Schrock group provided the opportunity to start applying olen metathesis to the synthesis of functionalized small molecules. When Greg Fu arrived at Caltech as a postdoctoral fellow, he accepted the challenge of demonstrating the application of well-dened olen metathesis catalysts (that were being explored as polymerization initiators) to the synthesis of small molecules. In a reasonably short period of time, he demonstrated that the tungsten and molybdenium alkylidenes would induce the ring closing metathesis for the formation of 5, 6 and 7 membered rings.39 The molybdenum system was particularly active and tolerated a range of functionality. This work introduced olen metathesis to the synthetic organic chemist.40 The full value of this reaction was not realized until catalysts41 were available that could be used with standard organic techniques and tolerated a broad range of functional groups. During the mid 80s, research that led to the development of ruthenium-based catalysts was initiated. Based on models, it was proposed that the polymers prepared from 7-oxonorbornene derivatives might be good ionophores. Bruce Novak set out to prepare such systems using the titanium and tungsten catalysts available at the time. After nding that none of the known catalysts worked for these systems, he explored the ill-dened catalysts that were

Scheme 6.

Scheme 7.

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prepared from late metal salts. He found that ruthenium trichloride polymerized olens and would even generate high molecular weight polymers in water.42 It was assumed that these catalyst systems operated by the same mechanism as the early metal cases and, therefore, had to involve a metal carbene. If this were the case it would have to be different from the alkylidene complexes known at the time and be stable both in water and show low sensitivity to oxygen. Novaks mechanistic studies demonstrated that a strained olen and ruthenium(II) were the keys to the formation of an active catalyst. These were the important observations that were essential for the later synthesis of a well-dened catalyst.43 Sonbihn Nguyen took on the challenge of determining whether a well-dened, active ruthenium carbene catalyst could be prepared. Combining the need for ruthenium(II) observed by Novak with the experience of Lynda Johnston in developing routes to the formation of tungsten carbenes44 using cyclopropenes, Nguyen reacted a ruthenium(II) complex with diphenylcyclopropene. This reaction resulted in a stable 16 e2 ruthenium carbene complex that was not only active towards the polymerization of norbornene but was also stable in the presence of protic solvents!45 The basic structure of the active bis(triphenylphosphine)dichlororuthenium alkylidene complex has remained the same in even the most recent highly active catalysts. The bis(triphenylphosphine) complex (6) was only active for metathesis with strained and electron rich olens. It would not polymerize cis-cyclooctene although it would polymerize trans-cycloooctene. In order to increase the activity of the catalysts, ligand exchanges were carried out. The lessons learned from the Schrock group suggested that activity increased as the metal center became more electrophylic.46 Consequently, the anionic ligands were modied or ionized to form cationic complexes in an attempt to afford more active systems.47 In frustration, Nguyen carried out the opposite ligand exchange and substituted the more basic cyclohexylphosphine ligand.48 This change produced the desired reactivity (Scheme 8). The complex with the more basic ligand (7) would now polymerize unstrained olens and induce reactions with acyclic olens.49 Greg Fu demonstrated that these ruthenium-based systems (7) would promote many of the same reactions as the Schrock molybdenum-based alkylidene complexes but had greater functional group tolerance and could be handled using standard organic techniques.50 The early transition metalbased catalysts required vacuum line and dry box conditions for efcient use in organic reactions whereas the ruthenium catalysts could be handled in air as solids and the reactions were carried out under a nitrogen atmosphere in standard asks. Although there have been many demonstrations of the

tolerance of these catalysts to functional groups, the ring closing reactions of highly functionalized polypeptides by Miller and Blackwell51 provide some of the most striking examples. In contrast to the usual direction of technology ow, this is a case where a reaction developed for polymerization chemistry became important in organic synthesis. The ability to promote metathesis polymerization without the processing concerns of the early classical catalysts opened a number of new applications. One group initiated studies of the ruthenium-based catalysts in the polymerization of dicyclopentadiene. Polydicyclopentadiene is a commercial material that is made by a reaction injection molding (RIM) process from tungsten and molybdenum complexes that are combined with alkylaluminums. These processes required protection from air and water, and did not tolerate impurities and additives in the monomer. The ruthenium systems allowed many of these problems to be overcome.52 After the early papers on the ruthenium chemistry, a number of researchers inquired about obtaining samples of the complex. Until a commercial source could be developed, limited samples were provided to the community for testing. John Birmingham of Boulder Scientic obtained the license for the manufacture of the catalyst and aided in the development of the technology by providing substantial volumes of catalyst to organic and polymer chemists. The technology was subsequently licensed to Materia, Inc., who now exclusively manufactures the catalysts and distributes them through Sigma-Aldrich. As the need for larger quantities of catalyst grew, more efcient methods for its synthesis were required. The cyclopropene route was useful for the preparation of the catalyst on the gram scale but was very difcult to scale-up. Marcia France initiated work on the use of diazo compounds as initiators for the ill-dened catalysts and demonstrated that stable ruthenium complexes could be prepared by such reactions. Peter Schwab developed an excellent route to the preparation of the ruthenium benzylidene complexes and demonstrated the high activity and rapid initiation of this family of catalysts.53 These complexes have served as the basis for the development of the ruthenium metathesis technology (Scheme 9).

Scheme 9.

Key to their commercialization was the development of a method to safe and efcient scale-up the diazo route by Mike Giardello. A one pot synthesis of an active derivative

Scheme 8.

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was later developed by Tomas Belderrain and Tom Wilhelm (Scheme 10).54

Scheme 10.

This route, which produces catalyst in over 90% yields from ruthenium chloride, has been used to prepare many kilos of the catalyst. The commercial availability of the ruthenium catalyst made its widespread use possible. Recent reviews55 describe a wide variety of applications that range from the synthesis of pharmaceutical intermediates to the production of a variety of polymer composites.56 As had been demonstrated earlier, the ruthenium systems derived from ruthenium salts were active in water. By designing the appropriate water soluble ligands, an active water soluble ruthenium based olen metathesis catalyst was prepared that produced living polymers in water.57 The instability of these systems limited their activity in reactions involving unstrained olens.58 Essential for all of our work has been the understanding of the fundamental reaction pathways for catalysis. Eric Dias initiated a detailed study of the mechanism of metathesis using ruthenium catalysts.59 The key nding was that the reaction proceeded by the lose of one of the neutral ligands to produce a 14 e2 species. It was proposed that the higher activity of the more basic phosphine was a result of stabilization of the intermediate metallacycle since progressing from the carbene olen complex to the metallacycle involved oxidation of the metal center in addition to favoring the addition of a p-acidic olen (Scheme 11).

of the catalyst was insufcient to give high yields of products with reasonable catalyst loadings. A study of the thermal reactions of ruthenium alkylidene complexes was initiated to determine the decomposition modes at normal reaction temperatures. Mike Ulman found that substituted alkylidenes decomposed by a bimolecular mechanism that involved the loss of phosphine. Consequently, any technique that increased the rate of phosphine loss would also increase the rate of catalyst decomposition. In fact, productive metathesis is rst order while decomposition is second order in the 14 e2 species. The parent methylene complex decomposed in a rst order phosphine independent mechanism. Under many conditions, the methylene decomposition is the efciency determining reaction. This set of observations indicated that the tricyclohexylphosphine complex was the optimum phosphine based system. Although a number of techniques utilizing chelating ligands gave some slight improvements in stability,60 a new ligand system was required for the next breakthrough. Herrmann61 and others demonstrated62 that the substitution of phosphines in catalyst systems with stabile N-heterocyclic carbenes produced interesting changes in reactivity. In 1998, his group reported that complex (9), in which both phosphines of 8 had been replaced by dialkyl imidazolin-2ylidene ligands, gave a catalyst with superior activity to that of 8.63 Although these catalysts did not turn out to be more active than the phosphine systems,64 the fact that they showed any activity at all even though the NHC ligands were less labile than the phosphines suggested that they might be interesting ligands (Scheme 12).

Scheme 12.

Our group then launched a program to synthesize analogs of 8 by substitution of the phosphines with NHCs. More than 10 different ligand systems were examined. Arduengos most stable NHC that substituted with mesityl groups, 1,3dimesitylimidazolin-2-ylidene turned out to be the key ligand. Other alkyl-substituted NHCs or aromatic-substituted NHCs without ortho substituents either would not substitute for the phosphine, decomposed rapidly, or gave double substitution. The mesityl substituted ligandnow called Imesgave a stable system in which only one of the phosphines was substituted by an NHC.65 This complex (10), also reported by the Nolan66 and the Herrmann67 groups, shows high activity and stability. The NHC provided a strong electron donor to stablize the intermediates and the phosphine provide the labile
Scheme 11.

Less bulky basic phosphines coordinated too strongly to the metal and were not susceptible to dissociation/initiation. Phosphines with a larger cone angle than cyclohexylphosphine were too labile to produce a stable complex. In a number of difcult ring-closing reactions, the lifetime
Scheme 13.

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R. H. Grubbs / Tetrahedron 60 (2004) 71177140

ligand required for the formation of the 14 e2 species (Scheme 13). Building on our earlier work on the synthesis of chiral molybdenum68 based metathesis catalysts and the outstanding success of the Schrock and Hoveyda groups69 with later generation chiral catalysts, Mattias Scholl constructed a chiral NHC using the commercially available (1R,2R)diphenylethylenediamine. Palladium coupling with mesityl bromide gave the appropriate precursor for the formation of the dihydro-2-imidazazolium salt. The complex that resulted from the substitution of one of the phosphines by this ligand was unusually reactive. The rst attempted kinetic resolution was complete in the time period estimated from the reactions with the unsaturated analog. An undergraduate, Sheng Ding, prepared the parent achiral system (11) which was more active than 10 in most reactions and was much more stable than the phosphine analogs (Scheme 14).70

The titanium reagents helped to introduce metal alkylidenes to organic and polymer synthesis and served as mechanistic models. However, they were limited by functional group sensitivity and lack of reactivity. The Schrock molybdenum-based systems provided the rst catalysts that allowed for the general application of metathesis in organic synthesis and remain key reagents in a number of transformations. However, their sensitivity to air, water and some functional groups limited many of their applications. The initial ruthenium-based catalysts, due to their ease of use and broad functional group tolerance, opened the broad application of metathesis. However, their lack of reactivity limited by their utility. The recently developed NHC systems (10 and 11 and analogs) have increased reactivity and selectivity. A few of the broadening possibilities opened with recent catalyst developments will be discussed below. Cross metathesis has seen limited use due to the statistical yield of products observed in cross reactions of simple olens. The yield of the desired cross product is limited to 50% of a thermodynamic ratio of E:Z isomers when the olens are used in a 1:1 ratio.75 However, with the more active NHC-substituted catalysts, a number of more highly functionalized olens were found to undergo clean metathesis reactions. Arnab Chatterjee developed a set of guidelines for the prediction of the outcome of cross metathesis reactions.76 Key to this analysis was the nding that there is a wide variety of olens that will take part in cross metathesis with alkyl-substituted olens (Type 1) but undergo homometathesis at a much slower rate. Those olens are classied at Type 2 or 3 depending on the reactivity of the pseudo-dimer. In those circumstances where a Type 1 olen reacts with a Type 2 or 3 olen and the reaction is pushed to completion so that all of the methylenes are released as ethylene, the less reactive partner must react with the more reactive partner to give the cross product as the dominate product. Steric bulk in the allylic position, as well as alkyl substitution directly on the double bond greatly reduces the rate of homodimerization and such olens are classied as Type 2 or 3. For example, the ketal of methylvinylketone gives a near quantitative yield of the cross product. Steric bulk also favors the E isomer (Scheme 15). In a similar way, isobutylene and other 2-substituted olens undergo slow dimerization to the tetrasubstituted double bond. When reacted with a terminal olen, the trisubsituted olen is favored. To increase the rate of reaction, the 2-substituted olen is used in large excess. With isobutylene, isoprenoid groups, a general structure in terpenes, is easily installed (Scheme 16).77

Scheme 14.

Based on the earlier mechanistic work that demonstrated that activity required the loss of one of the neutral ligands, it was assumed that the increased activity of the NHC systems was a result of the NHC ligands strong s-donating ability and the resulting strong trans effect. Detailed mechanistic studies by Melanie Sanford demonstrated that the rate of formation (k1) of the 14 e2 species was actually 102 slower for the NHC systems.71 The increase in rate was the result of the favored reaction of the p acidic olen relative to other s-donors in the system. For example, the reaction of ethylvinyl ether with the intermediate 14 e2 complex is 104 times faster (k21/k2) than with tricyclohexylphosphine. It is this increased reactivity with p acids that accounts for the higher activity of the NHC analogs in olen metathesis.72 Variations on these structures show improved activity for some applications. As will be seen later, the extremely active bispyridine analogs73 have applications in polymer synthesis and it has been found that the chelating ether systems of Hoveyda74 have applications in some difcult organic transformations. Although there are now many variations of the catalyst structures, it is interesting that the basic ligand array has remained that initially discovered by Nguyentwo trans neutral ligands, two halogens and the alkylidene around a ruthenium center. Each improvement in catalysts reactivity and selectivity has led to a variety of new applications and synthetic strategies.

Scheme 15.

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inserts into the polymer chain to release the methylenes as ethylene. The lack of homodimerization of acrylates results in an alternating structure when the monomers are present in precisely a 1:1 ratio. In addition to the opportunities opened by the functional group and oxygen/water tolerance of the ruthenium catalysts in organic synthesis, these features also provide many new polymer synthesis and processing possibilities.80 As with other polymerizations of norbornene with welldened catalysts, the ruthenium systems are living. However, in spite of the fact that the growing chains are stable and do not undergo backbiting reactions at a competitive rate, the polydispersity of many of the polymers is broad due to slow initiation of the catalyst. As discussed above, the mechanism of action of these complexes is the loss of one of the neutral ligands. Consequently, the control of the polydispersity is associated with the rate of ligand loss, k1, and the rate of propagation k2.81 The polydispersity of the polymers prepared with 8 could be narrowed by adding excess triphenylphosphine, a ligand that has a larger k1 than the cyclohexylphosphine ligand and also traps the 14 e2 species (Scheme 19).82 In contrast, the NHC initiator 11 could not be controlled by phosphine addition. As found in the mechanistic studies, the NHC systems showed very high rates of metathesis but unexpectedly low rates of ligand lossi.e. initiationto form the 14 e2 species. While examining the rates of ligand loss in the mechanistic studies, it was found that the easily formed bispyridine derivatives showed very high exchange rates. These derivatives employ two pyridine ligands on the ruthenium in place of one tricyclohexylphosphine. Their reactivity could be tuned by adding substituents to the pyridine ligands. In the end, the bis(3-bromopyridine)

Scheme 16.

Electron decient double bonds showed very low reactivity with the bis(phosphine) family of catalysts. For example, the metathesis of a mixture of 6-acetoxy-1-hexene with methylacrylate using 8 as the catalyst gave only the dimer of the hexene. The acrylate neither reacted nor hindered the dimerization reaction. However, Chatterjee found a similar reaction with the NHC catalyst 11 gave a .90% yield of the cross product the substituted acrylate (Scheme 17).78 Reaction with electron decient double bonds is a general feature of these catalysts. The greater electron donating ability of the NHC relative to tricyclohexylphosphine results in excellent reactivity with the more p-acidic acrylates. For example, the reaction of alkyl substituted olens with crotonaldehyde provides a very efcient route to a,b-unsaturated aldehydes. These products are key intermediates in a variety of transformations including the MacMillan organocatalysis reactions.79 The same factors that give high yields of cross products in small molecules, lead to the formation of alternating polymers when a cyclic olen is reacted with a diacrylate (Scheme 18). Following the reaction by NMR shows that the cyclic olen polymerizes rst and the electron decient olen then

Scheme 17.

Scheme 18.

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R. H. Grubbs / Tetrahedron 60 (2004) 71177140

Scheme 19.

Mes N

NCH3 + Br O

N Mes Cl N Ru CHPh Cl N Br 12

O Ph O O N Me
EtOCH2=CH2

n [Ru]

OBn OBn Ph O

O n N Me O BnO
m

[Ru]

OBn

EtOCH2=CH2

Mn= 10 K PDI= 1.05

Scheme 20.

Mn=73K PDI=1.07

adduct (12) was found to provide optimum levels of reactivity. The pyridines exchange about 103 times faster than the tricyclohexylphosphine ligands. Using the bis(3-bromopyridine) complex as the initiator for the polymerization of a variety of norbornene derivatives produced polymers with narrow polydispersities and allowed the formation of multiblock copolymers. Quenching of the living polymers with ethylvinyl ether resulted in low dispersity homo and block copolymers (Scheme 20).83 The strong complexing ability of the NHC ligand opened the opportunity to prepare a new class of polymers. Cyclic polymers have been of interest for many years. Since the properties of linear polymers are best described using reptation theory, the understanding of mobility of an

endless, cyclic polymer requires a route to prepare pure cycles on a scale large enough for detailed study. Metathesis provides such a possibility. By chelating the carbene to the NHC ligand a catalyst (13) is formed that is cyclic. Insertion of a cyclic olen results in the growth to a larger cycle (Scheme 21). Backbiting chain transfer can compete with chain growth to bite off a portion of the ring and produce a cycle. It is fortunate that chain growth is much faster than chain transfer and the backbiting appears to occur near the ligand to produce large rings. With cyclooctene as the monomer, n) of .100 K polymers with average molecular weights (M can be produced.84 Detailed studies of the physical properties of this fundamentally interesting class of polymers are now being carried out.

Scheme 21.

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Following the development of olen metathesis from an interesting reaction that was only useful for unfunctionalized olens, used ill-dened catalysts, and proceeded by a totally unknown mechanism to the present highly active, well-dened, functional group tolerant, and mechanistically well understood catalyst systems has been fun. A number of times along the way, I thought the journey was complete. However, the reaction keeps fooling me. It will be interesting to see where it leads next.

18. 19. 20. 21. 22.

References and notes

1. Ivin, K. J.; Mol, J. C. Olen Metathesis and Metathesis Polymerzation; Academic: New York, 1997. 2. Bands, R. L.; Bailey, G. C. Ind. Eng. Chem., Prod. Res. Dev. 1964, 170. 3. This is intended to be a personal account and reference will be made to that work that had a major inuence on the progress of the research in my group and I apologize for any omissions. A few of the high-light papers that impacted the development of metathesis catalysts in our group will be discussed. I wish to thank the over 200 researchers who have contributed to my work over the years. The major emphasis will be on the path of catalyst development. 4. Calderon, N.; Chen, H. Y.; Scott, K. W. Tetrahedron Lett. 1967, 3327. 5. Grubbs, R. H.; Brunck, T. K. J. Am. Chem. Soc. 1972, 94, 2538. Lewandos, G. S.; Pettit, R. J. Am. Chem. Soc. 1971, 93, 7087. 6. An out growth of our work with metallacyclopentanes lead to the detailed study of metallacyclopentanes of nickel and platinum by Professor Akira Miyashita, deceased November 2003 Grubbs, R. H.; Miyashita, A.; Liu, M.; Burk, P. J. Am. Chem. Soc. 1977, 99, 3863. 7. Herisson, J.-L.; Chauvin, Y. Makromol. Chem. 1971, 141, 161. 8. Casey, C. P.; Burkhard, T. J. J. Am. Chem. Soc. 1973, 95, 5833 5834. Casey, C. P.; Burkhard, T. J. J. Am. Chem. Soc. 1974, 96, 7808 7809. 9. Schrock, R. R. J. Am. Chem. Soc. 1974, 96, 6796 6797. 10. Katz, T. J.; McGinnis, J. J. Am. Chem. Soc. 1975, 97, 1592 1594, By measuring the cross over products as a function of time, the ratio of products could be obtained at zero time. In this publication, the mechanism for acetylene metathesis was also proposed. 11. Grubbs, R. H.; Burk, P. L.; Carr, D. D. J. Am. Chem. Soc. 1975, 97, 3265. A footnote to the paper in Ref. 10 above was added in proof to this paper. 12. Katz, T. J.; Rothchild, R. J. Am. Chem. Soc. 1976, 98, 2519 2526. 13. Grubbs, R. H.; Carr, D. D.; Hoppin, C.; Burk, P. L. J. Am. Chem. Soc. 1976, 98, 3478. 14. Katz, T. J.; McGinnis, J. J. Am. Chem. Soc. 1977, 99, 1903. 15. Michelotti, F. W.; Keaveney, W. P. J. Polym. Sci. 1965, A3, 895. 16. Schrock, R. R. Acc. Chem. Res. 1979, 12, 98 104, Alkoxide substitution on the systems converted a number of the early halide complexes into active metathesis catalysts. Schrock, R. R.; Rocklage, S.; Wengrovius, J.; Rupprecht, G.; Fellmann, J. J. Mol. Catal. 1980, 8, 73. 17. Katz, T. J.; Lee, S. J.; Acton, N. Tetrahedron Lett. 1976, 47,

23. 24. 25. 26. 27. 28.

29.

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40.

41.

4247. See Ref. 6 of Katz, T. J.; Ho, T. H.; Shih, N. Y.; Ying, Y. C.; Stuart, V. J. Am. Chem. Soc. 1984, 106, 2659 2668. Lee, S. J.; McGinnis, J.; Katz, T. J. J. Am. Chem. Soc. 1976, 98, 7818. Katz, T. J.; Acton, N. Tetrahedron Lett. 1976 , 47, 4251 4254. Tebbe, F. N.; Parshall, G. W.; Ovenall, D. W. J. Am. Chem. Soc. 1979, 101, 5075. Wengrovius, J.; Schrock, R. R.; Churchill, M. R.; Missert, J. R.; Youngs, W. J. J. Am. Chem. Soc. 1980, 102, 4515. Kress, J. R. M.; Russell, M. J.; Wesolek, M. G.; Osborn, J. A. Chem. Commun. 1980, 431 432. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Chem. Soc. 1978, 100, 3611. Pine, S. H.; Zahler, R.; Evans, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 1980, 102, 3270. Howard, T. R.; Lee, J. B.; Grubbs, R. H. J. Am. Chem. Soc. 1980, 102, 6876. Lee, J. B.; Ott, K. C.; Grubbs, R. H. J. Am. Chem. Soc. 1982, 104, 7491. Kress, J.; Osborn, J. A.; Greene, R. M. E.; Ivin, K. J.; Rooney, J. J. J. Am. Chem. Soc. 1987, 109, 899. Wengrovius, J. H.; Schrock, R. R.; Churchill, M. R.; Missert, J. R.; Youngs, W. J. J. Am. Chem. Soc. 1980, 102, 4515 4516. Quignard, F.; Leconte, M.; Basset, J.-M. J. Mol. Catal. 1986, 36, 3. Couturier, J. L.; Paillet, C.; Leconte, M.; Basset, J. M.; Weiss, K. Angew. Chem., Int. Ed. Engl. 1992, 31(5), 628 631. Schrock, R. R.; DePue, R. T.; Feldman, J.; Schaverien, C. J.; Dewan, J. C.; Liu, A. H. J. Am. Chem. Soc. 1988, 110, 1423 1435. Schrock, R. R.; Feldman, J.; Cannizzo, L. F.; Grubbs, R. H. Macromolecules 1987, 20, 1169. Klavetter, F. L.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 7807 7813. Swager, T. M.; Dougherty, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 2973 2974. Gilliom, L. R.; Grubbs, R. H. J. Am. Chem. Soc. 1986, 108, 733 742. Gilliom, L. R.; Grubbs, R.H.; Gilliom, L. R. Proceedings of the Fourth International Symposium on Homogeneous Catalysis, Leningrad, USSR, Sept 24 28, 1984. Diphenylcyclopropene would be an important reagent later in our development of the ruthenium based catalysts. My involvement with arylcyclopropenes goes back to my Masters research with Merle Battiste at the University of Florida. Gilliom, L. R.; Grubbs, R. H. Organometallics 1986, 5, 721. Cannizzo, L. F.; Grubbs, R. H. Macromolecules 1987, 20, 1488 1490. Risse, R. H.; Grubbs, R. H. Macromolecules 1989, 22, 1558 1562. Stille, J. R.; Grubbs, R. H. J. Am. Chem. Soc. 1986, 108, 855. Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 5426 5427. Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114(18), 7324 7325. Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 3800 3801. Martin, S.; Liao, Y.; Rein, T. Tetrahedron Lett. 1994, 35, 691. Borer, B.; Deerenberg, S.; Bierougel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191. Houri, A.; Xu, Z.; Cogan, D.; Hoveyda, A. J. Am. Chem. Soc. 1995, 117, 2943. Furstner, A.; Langermann, K. J. Org. Chem. 1996, 3942. See for early demonstrations of ring closing metathesis using

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42. 43. 44. 45. 46. 47. 48. 49.

50. 51.

52.

53.

54. 55. 56. 57.

58. 59. 60.

61. 62.

63.

64.

classical catalysts Villemin, D. Tetrahedron Lett. 1980, 1715. Tsuji, J.; Hashiguchi, S. Tetrahedron Lett. 1980, 2955. Novak, B. M.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 960 961. Novak, B. M.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 7542 7543. Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 8130 8145. Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3974 3975. Schaverien, C. J.; Dewan, J. C.; Schrock, R. R. J. Am. Chem. Soc. 1986, 108, 2771 2773. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503 5511. Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858 9859. Demonceau, A.; Noels, A. F.; Saive, E.; Hubert, A. J. J. Mol. Catal. 1992, 776, 123 132, Demonstrated that ruthenium(II) salts mixed with diazo alkanes would yield metathesis products in the presence of tricyclohexylphosphine. Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9856 9857. Miller, S. J.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 5855 5856. Blackwell, H. E.; Grubbs, R. H. Angew. Chem., Int. Ed. 1998, 37(23), 3281 3284. Charles Woodson started Advanced Polymer Technologies (now Cymetech) to develop ruthenium based polyDCPD technology. Commercial products are now being marketed based on this technology. Schwab and France Schwab, P.; France, M. B.; Ziller, J. W. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039 2041, Angew. Chem. 1995, 107, 2179 2181. Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100 110. Wilhelm, T. E.; Belderrain, T. R.; Brown, S. N.; Grubbs, R. H. Organometallics 1997, 16(18), 3867 3869. Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: New York, 2003; p 214 Chapter 2.14. Ref. 52, Chapter 3.12. For example a polymer reinforced baseball bat is being marketed by Easton Sports. Lynn, D. M.; Kanaoka, S.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 784 790. Lynn, D. M.; Mohr, B.; Grubbs, R. H. J. Am. Chem. Soc. 1998, 120, 1627 1628. Kirkland, T. A.; Lynn, D. M.; Grubbs, R. H. J. Org. Chem. 1998, 63(26), 9904 9909. Dias, L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887 3897. Chang, S.; Jones, L., II; Wang, C.; Henling, L. M.; Grubbs, R. H. Organometallics 1998, 17(16), 3460 3465. Dias, E. L.; Grubbs, R. H. Organometallics 1998, 17(13), 2758 2767. Herrmann, W. A.; Elison, M.; Fischer, J.; Kocher, C.; Artus, G. R. J. Angew. Chem., Int. Ed. Engl. 1995, 21, 2371 2374. It is interesting that the earliest demonstration of a carbene metathesis mechanism was by M.F. Lappert using N-heterocyclic carbenes Cardin, D. J.; Doyle, M. J.; Lappert, M. F. Chem. Commun. 1972, 16, 927. He also demonstrated that NHCs were ligands that showed many of the same features as phosphines. Cardin, D. J.; Cetinkkay, B.; Lappert, M. F. Chem. Rev. 1972, 5, 545. Weskamp, T.; Schattenmann, W. C.; Spiegler, M.; Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1998, 37, 2490 2493. Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1999, 38, 262 262.

65. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 2247 2250. 66. Huang, J. K.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem. Soc. 1999, 121, 2674 2678. 67. Frenzel, U.; Weskamp, T.; Kohl, F. J.; Schattenman, W. C.; Nuyken, O.; Herrmann, W. A. O. J. Organomet. Chem. 1999, 2, 263265. 68. Fujimura, O.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 2499 2500. Fujimura, O.; Grubbs, R. H. J. Org. Chem. 1998, 63(3), 824 832. 69. Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251 8259. 70. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1(6), 953 956. 71. Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 749 750. 72. Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543 6554. 73. Bielawski, C. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 2000, 39(16), 2903 2906, Angew. Chem. 2000, 112(16) 3025 3028. 74. Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791 799. 75. Blackwell, H. E.; OLeary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58 71. OLeary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 7427 7430. 76. Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360 11370. Chatterjee, A. K.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 2003, 41 (17), 3171 3174, Angew. Chem. 2002 , 114 (17), 3303 3306. 77. Spessard, S. J.; Stoltz, B. M. Org. Lett. 2002, 1, 1943 1946. 78. Chatterjee, A. K.; Grubbs, R. H. Org. Lett. 1999, 1(11), 1751 1753. Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122(15), 3783 3784. 79. Austin, J. F.; MacMillan, D. W. C. J. Am. Chem. Soc. 2002, 124(7), 1172 1173. 80. Ref. 47, Chapter 3.12. 81. Robson, D. A.; Gibson, V. C.; Davies, R. G.; North, M. Macromolecules 1999, 32, 6371. 82. Bielawski, C.; Grubbs, R. H. Macromolecules 2001, 34(26), 8838 8840. 83. Choi, T.-L.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 2003, 42, 1743 1746. 84. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002, 297, 2041 2044.

Publication list of Robert H. Grubbs 1966 to present

1. Battiste, M. A.; Halton, B.; Grubbs, R. Thermal rearrangements in the tetra-arylcyclopropene series. Chem. Commun. 1966, 907. 2. Grubbs, R.; Breslow, R.; Herber, R.; Lippard, S. J. Studies of iron tricarbonyl cyclooctatetraene complexes. J. Am. Chem. Soc. 1967, 89, 6864. 3. Breslow, R.; Grubbs, R.; Marahashi, S.-I. Electrochemical evidence for the antiaromaticity of cyclobutadiene. J. Am. Chem. Soc. 1970, 92, 4139.

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4. Grubbs, R. H. Cyclobutadieneiron tricarbonyl complexes. J. Am. Chem. Soc. 1970, 92, 6693. 5. Grubbs, R. H.; Kroll, L. C. Catalytic reduction of olens with a polymer supported rhodium(I) catalyst. J. Am. Chem. Soc. 1971, 93, 3062. 6. Grubbs, R. H.; Kroll, L. C. The selectivity of polymer supported homogeneous catalysts. Presented at the 162nd ACS Meeting, Washington, DC, 1971. Special Symposium on Polymers as Reagents. Polymer Preprints, 1971. 7. Grubbs, R. H.; Brunck, T. K. A possible intermediate in the tungsten catalyzed olen metathesis reaction. J. Am. Chem. Soc. 1972, 94, 2538. 8. Grubbs, R. H. Polymer supported rhodium(I) hydrogenation catalysts: factors controlling substrate selectivity. Presented at the 164th ACS meeting. Polymer Preprints 1972, 46. 9. Grubbs, R.; Grey, R. A. Chiral tricarbonyl cyclobutadieneiron complexes. Chem. Commun. 1973, 76. 10. Grubbs, R.; Gibbons, C.; Kroll, L. C.; Bonds, W. D.; Brubaker, Jr. C. H. Activation of homogeneous catalysis of polymer attachment. J. Am. Chem. Soc. 1973, 95, 2373. 11. Grubbs, R. H. Polymer attached homogeneous hydrogenation catalysts. Polym. Prepr. 1973, 30. 12. Grubbs, R. H.; Kroll, L. C.; Sweet, E. M. The preparation and selectivity of polymer attached rhodium(I) olen hydrogenation catalysis. J. Macromol. Sci. Chem. 1973, A7, 1047. 13. Grubbs, R. H.; Grey, R. A. Cyclobutadiene as an intermediate in the oxidative decomposition of cyclobutadienyliron tricarbonyl. J. Am. Chem. Soc. 1973, 95, 5765. 14. Bieeld, C. G.; Eick, H. A.; Grubbs, R. H. Crystal structure of bis(triphenylphosphine)tetramethylkene platinum(II). Inorg. Chem. 1973, 12, 2166. 15. Breslow, R.; Muriayama, D. R.; Murahashi, S. I.; Grubbs, R. H. Quantitative assessment of the antiaromaticity of cyclobutadiene by electrochemical studies on quinone derivatives. J. Am. Chem. Soc. 1973, 95, 6688. 16. Grubbs, R. H.; Pancoast, T. A.; Grey, R. A. Intramolecular trapping of cyclobutadiene. Tetrahedron Lett. 1974, 2425. 17. Bonds, W. D.; Brubaker, C. H.; Chndrasekaran, E. S.; Gibbons, C.; Grubbs, R. H.; Kroll, L. C. Polystyrene attached titanocene species, preparation and reactions. J. Am. Chem. Soc. 1975, 97, 23128. 18. Grubbs, R. H.; Burk, P. L.; Carr, D. D. Consideration of the mechanism of the olen metathesis reaction. J. Am. Chem. Soc. 1975, 97, 3265. 19. Grubbs, R. H.; Carr, D. D.; Burk, P. L. Metallocycles as intermediates in organotransition-metal reactions. In Organotransition-metal Chemistry; Ishii, Y., Tsutsuii, M., Eds.; Plenum: New York, NY, 1975; p 135. 20. Grubbs, R. H.; Sweet, E. M. Microprobe analysis of polystyrene-attached catalysts. Macromolecules 1975, 8, 241. 21. Grubbs, R. H.; Burk, P. L.; Carr, D. D. Consideration of the mechanism of the olen metathesis reaction. J. Am. Chem. Soc. 1975, 97, 3265. 22. Grubbs, R. H.; Carr, D. D.; Hoppin, C.; Burk, P. L. Consideration of the mechanism of the metal catalyzed olen metathesis reaction. J. Am. Chem. Soc. 1976, 98, 3478. 23. The olen metathesis reaction; New applications of organometallic reagents in organic synthesis. Seyferth, D., Ed.; Elsevier: Amsterdam, 1976; p 423. 24. Grubbs, R. H.; Sweet, E. M.; Phisanbut, S. Polymer attached catalysts. In Catalysis in Organic Synthesis; Greeneld, Ed.; Academic, 1976; p 153.

25. Grubbs, R. H.; Chandrasekaran, E. S.; Brubaker, Jr. C. H. Polymer supported organometallic compounds of titanium, zirconium and hafnium as hydrogenation catalyst. J. Organomet. Chem. 1976, 120, 49. 26. Grubbs, R. H.; Su, S.-C. H. The preparation of polymeric organophosphorus ligands for catalyst attachment. J. Organomet. Chem. 1976, 122, 151. 27. Grubbs, R. H. Polymer attached homogeneous catalyst. Strem Chemiker 1976, 4, 3. 28. Grubbs, R. H.; Blackborow, J. R.; Miyashita, A.; Scrivanti, A. Chemical synthesis with metal atoms: the reaction of chromium and nickel atoms with styrene. J. Organomet. Chem. 1976, 120, C49. 29. Blackborow, J. R.; Grubbs, R. H.; Miyashita, A.; Scrivanti, A.; Koerner von Gustorf, E. A. Chemical synthesis with metal atoms: the reaction of 1,4- and 1,3-cyclohexadiene with chromium atoms and triuorophosphine. J. Organomet. Chem. 1976, 122, C6. 30. Grubbs, R. H.; Pancoast, T. A. Intramolecular trapping of cyclobutadiene complexes. J. Am. Chem. Soc. 1977, 99, 2382. 31. Grubbs, R. H.; Swetnick, S.; Su, S. C.-H. Hybrid catalystmetathesis catalysts attached to polystyrene copolymer. Proceedings of CNRS, No. 281 Relations Between Homogeneous and Heterogeneous Catalysis, Lyon 1977, 281, 3 6. 32. Grubbs, R. H.; Swetnick, S.; Su, S.-C. H. Hybrid catalystsmetathesis catalysts attached to polystyrene. J. Mol. Catal. 1977, 3, 11. 33. Grubbs, R. H.; Hoppin, C. R. Initiation of olen metathesis: reaction of deca-2,8-diene with catalysts formed from Me4Sn WCl6 (Ph3P)2(NO)2Mo. J. Chem. Soc., Chem. Commun. 1977, 634. 34. Grubbs, R. H.; Miyashita, A.; Liu, M.; Burk, P. The preparation and reactions of nickelocyclopentanes. J. Am. Chem. Soc. 1977, 99, 3863. 35. Grubbs, R. H.; Miyashita, A. The metallacyclopentane-olen interchange reaction. Chem. Commun. 1977, 864. 36. Grubbs, R. H.; Su, S.-C. H.; Sweet, E. M. Hybrid catalyst. Polym. Prepr. 1977. Spring ACS meeting. 37. Grubbs, R. H.; Lau, C. P.; Brubaker, C.; Cukier, R. Polymer attached metallocenes. Evidence for site isolation. J. Am. Chem. Soc. 1977, 99, 4517 4518. 38. Grubbs, R. H. Hybrid phase catalysts. Chemtech 1977, 512. 39. Grubbs, R. H.; DeVries, R. Asymmetric hydrogenation by an atropisomeric diphosphinite rhodium complex. Tetrahedron Lett. 1977, 1879. 40. Blackborow, J. R.; Grubbs, R. H.; Hidenbrand, K.; Koerner von Gustorf, E. A.; Miyashita, A.; Scrivanti, A. Mechanism of the uxional behavior in (1-5-h-cycloheptadienyl)-1-5-hcycloheptatrienyl)iron. J. Chem. Soc., Dalton Trans. 1977, 2205. 41. Grubbs, R. H.; Pancoast, T. A. The mechanism of the oxidative decomposition of cyclobutadienyliron tricarbonyl complexes. J. Am. Chem. Soc. 1977, 99, 2382. 42. Grubbs, R. H.; Sweet, E. M. Polymer attached catalysts; A comparison between polystyrene attached and homogeneous Rh(I) hydrogenation catalysts. J. Mol. Catal. 1977/78, 3, 259. 43. Grubbs, R. H. The olen metathesis reaction; Progress in Inorganic Chemistry, Lippard, S. J., Ed.; Wiley: New York, NY, 1978; Vol. 24. 44. Grubbs, R. H.; Miyasshita, A. The relationship between metallacyclopentanes and bis-olen-metal complexes. J. Am. Chem. Soc. 1978, 100, 1300.

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45. Grubbs, R. H.; Miyashita, A. In Metallacycles in Organotransition Metal Chemistry. 2nd International Symposium on Homogeneous Catalysts, Fundamental Research In Homogeneous Catalysis; Tsutsui, M., Ed.; 1978; Vol. 2. 46. Grubbs, R. H.; Su, S.-C. H. Organometallic polymers as catalysts. In Organometallic Polymer; Sheets, Pittman, Eds.; 1978; p 129. 47. Grubbs, R. H.; Pancoast, T. A. Preparation of cyclobutadienyliron tricarbonyl complexes using disodium tetracarbonyl ferrate (22). Synth. React. Inorg. Met.-Org. Chem. 1978, 8, 1. 48. Grubbs, R. H.; Miyashita, A.; Liu, M.; Burk, P. Preparation and reaction of phosphine nickelocyclopentanes. J. Am. Chem. Soc. 1978, 100, 2419. 49. Grubbs, R. H.; Miyashita, A. Preparation and isomerization reactions of 2-nickelahydrindanes. J. Organomet. Chem. 1978, 161, 371. 50. Grubbs, R. H.; Miyashita, A. Metallacycles as catalysts for the linear and cyclodimerization of olens. J. Am. Chem. Soc. 1978, 100, 7416. 51. Grubbs, R. H.; Miyashita, A. Carbon carbon bond cleavage reactions in the decomposition of metallacycles. J. Am. Chem. Soc. 1978, 100, 7418. 52. Grubbs, R. H.; Miyashita, A. Reactions of metallacycles of nickel, metallacyclopentanes, hexanes and butanes. Proceedings of 1st International Symposium on Homogeneous Catalysis, ACS Meeting, Corpus Christi, Texas; 1978. 53. Blackborrow, J. R.; Feldhoff, U.; Grevels, F.-W.; Grubbs, R. H.; Miyashita, A. Chemical synthesis with metal atoms. Cyclodimerization of norbornadiene via nickela-cyclopentane intermediates. J. Organomet. Chem. 1979, 173, 253. 54. Grubbs, R. H.; Hoppin, C. Consideration of the mechanism of the transition metal catalyzed olen metathesis reaction: metathesis of cis,cis-2,8-decadiene. J. Am. Chem. Soc. 1979, 101, 1499. 55. Grubbs, R. H. Mechanistic studies of olen metathesis. Lubrizol Award Symposium at the Joint ACS/Chemical Society in Japan, Honolulu, Hawaii; 1979. 56. Grubbs, R. H. On the mechanism of olen metathesis and cyclopropanation. J. Inorg. Chem 1979, 18, 2623. 57. Chang, B.-H.; Grubbs, R. H.; Brubaker, Jr. C. H. The preparation and some catalytic activity of polymer-supported h 5-cyclopentadienyl-rhodium and -cobalt dicarbonyls. J. Organomet. Chem. 1979, 172, 81. 58. Grubbs, R. H.; Swetnick, S. J. Mechanism of olen metathesis over a supported molybdenum catalyst. J. Mol. Catal. 1980, 8, 25. 59. Pine, S. H.; Zahler, R.; Evans, D. A.; Grubbs, R. H. Titaniummediated methylene transfer reactions. The direct conversion of esters to vinyl ethers. J. Am. Chem. Soc. 1980, 102, 3270. 60. Grubbs, R. H.; Hu, S.-C. Polymer-attached homogeneous catalysis. In Enzymic and Non-enzymic Catalysis; Dunnill, P., Wiseman, A., Blakebrough, N., Eds.; Ellis Horwood: England, 1980; pp 223 235. 61. Howard, T. R.; Lee, J. B.; Grubbs, R. H. Titana-metallacarbene-metallacyclobutane reactions: stepwise metathesis. J. Am. Chem. Soc. 1980, 102, 6876. 62. Lau, C.-P.; Chang, B.-H.; Grubbs, R. H.; Brubaker, Jr. C. H. Polymer-supported metallocenes and their applications to the catalysis of olen isomerization, oligomerization, epoxidation and dinitrogen xation reactions. J. Organomet. Chem. 1981, 214, 325.

63. Lee, J. B.; Gajda, G. J.; Schaefer, W. P.; Howard, T. R.; Ikariya, T.; Grubbs, R. H. Structures of titanacyclobutanes. J. Am. Chem. Soc. 1981, 103, 7358. 64. Doxsee, K. M.; Grubbs, R. H. Nucleophilic activation of co for reduction by hydrogen. J. Am. Chem. Soc. 1981, 103, 7696. 65. Ott, K. C.; Grubbs, R. H. 1,3-Dimetallacyclobutanes in metal-methylidene dimerization reactions. J. Am. Chem. Soc. 1981, 103, 5922. 66. Grubbs, R. H. Metathesis and ring-opening polymerization relationship to Ziegler Natta polymerization. Proceedings of the Transition Metal Catalyzed Polymerizations MMI International Symposium, Midland, Michigan 1981, 17 21, 1981. 67. Ott, K. C.; Lee, J. B.; Grubbs, R. H. Stereochemical consequence of the interaction of alkylaluminums with titanacyclobutanes and its relationship to the olen metathesis reaction. J. Am. Chem. Soc. 1982, 104, 2942. 68. Grubbs, R. H. Alkene and alkyne metathesis reactions. Comprehensive Organomet. Chem. 1982. Chapter 54. 69. Soto, J.; Steigerwald, M.; Grubbs, R. H. Concerning the mechanism of Ziegler Natta polymerization: isotope effects of propagation rates. J. Am. Chem. Soc. 1982, 104, 4479. 70. Lee, J. B.; Ott, K. C.; Grubbs, R. H. Kinetics and stereochemistry of the titanacyclobutane-titanamethy-lene interconversion. Investigation of a degenerate olen metathesis reaction. J. Am. Chem. Soc. 1982, 104, 7491. 71. Straus, D. A.; Grubbs, R. H. Preparation and reaction of metal ketene complexes of Zr and Ti. J. Am. Chem. Soc. 1982, 104, 5499. 72. Ozawa, F.; Yamamoto, A.; Ikariya, T.; Grubbs, R. H. Photolysis and photo-induced isomerization of cis- and transdiethyl-bis(tertiary phosphine)palladium(II). Organometallics 1982, 1, 1481. 73. Straus, D. A.; Grubbs, R. H. Titanacyclobutanes: substitution pattern and stability. Organometallics 1982, 1, 1658. 74. Moore, E. J.; Straus, D. A.; Armantrout, J.; Santarsiero, B. D.; Grubbs, R. H.; Bercaw, J. E. Synthesis and structure of ketene complexes of permethylzirconocene and their hydrogenation to zirconium enolate hydrides. J. Am. Chem. Soc. 1983, 105, 2068. 75. Stille, J. R.; Grubbs, R. H. Synthetic applications of titanocene methylene complexes; selective formation of ketone enolates and their reactions. J. Am. Chem. Soc. 1983, 105, 1664. 76. Buchwald, S. L.; Grubbs, R. H. A titanium vinylidene route to substituted allenes. J. Am. Chem. Soc. 1983, 105, 5490. 77. Brown-Wensley, K. A.; Buchwald, S. L.; Cannizzo, L. F.; Clawson, L. E.; Ho, S. C. H.; Meinhardt, D. J.; Stille, J. R.; Straus, D. A.; Grubbs, R. H. Cp2TiCH2 complexes in synthetic applications. Pure Appl. Chem. 1983, 55, 1733. 78. Komiya, S.; Katoh, M.; Ikariya, T.; Grubbs, R. H.; Yamamoto, T.; Yamamoto, A. Reverse methyl migration from a methyl-iron complex to trimethyl-aluminum forming an ionic complex [Fe(Dmpe)2(acac)]AlMe2 4 . Organometallics 1984, 115. 79. Ott, K. C.; deBoer, E. J. M.; Grubbs, R. H. An investigation of the reaction of bis-cyclopentadienyltitanium dichlorides with trimethylaluminum. Mechanism of an a-hydrogen abstraction reaction. Organometallics 1984, 3, 223. 80. Mackenzie, P. B.; Ott, K. C.; Grubbs, R. H. Preparation of heteronuclear bridging methylene complexes. Pure Appl. Chem. 1984, 56, 59.

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metathesis polymerization (ROMP) of substituted cyclooctatetraenes. J. Am. Chem. Soc. 1993, 115, 4705 4713. Conticello, V. P.; Gin, D. L.; Grubbs, R. H. Ring-opening metathesis polymerization of substituted bicyclo[2.2.2]octadienes: a new precursor route to poly(1,4-phenylenevinylene). J. Am. Chem. Soc. 1992, 114, 9708 9710. Gorman, C. B.; Ginsburg, E. J.; Grubbs, R. H. Soluble, highly conjugated derivatives of polyacetylene from the ringopening metathesis polymerization of monosubstituted cyclooctatetraenes: synthesis and the relationship between polymer structure and physical properties. J. Am. Chem. Soc. 1993, 115, 1397 1409. McGrath, D. V.; Grubbs, R. H. The mechanism of aqueous ruthenium(II)-catalyzed olen isomerization. Organometallics 1994, 13, 224 235. Gagne, M. R.; Grubbs, R. H.; Feldman, J.; Ziller, J. W. Catalytic activity of a well dened binuclear ruthenium alkylidene complex. Organometallics 1992, 11, 3933 3935. Hillmyer, M. A.; Grubbs, R. H. The preparation of hydroxytelechelic poly(butadiene) via ring-opening metathesis polymerization employing a well-dened metathesis catalyst. Macromolecules 1993, 26, 872 874. France, M. B.; Grubbs, R. H.; McGrath, D. V.; Paciello, R. A. Chain transfer during the aqueous ring-opening metathesis polymerization of 7-oxanorbornene derivative. Macromolecules 1993, 26, 4742 4747. Grubbs, R. H.; Kratz, D. Highly unsaturated oligomeric hydrocarbons: a-(phenylethynyl)-v-phenylpoly[1,2-phenylene(2,1-ethynediyl)]. Chem. Ber. 1993, 126, 149 157. Fu, G. C.; Grubbs, R. H. The synthesis of cycloalkenes via alkylidene-mediated olen metathesis and carbonyl olenation. J. Am. Chem. Soc. 1993, 115, 3800 3801. Fisher, R. A.; Grubbs, R. H. Ring-opening metathesis polymerization of exo-dicyclopentadiene: reversible crosslinking by a metathesis catalyst. Makromol. Chem. Macromol. Symp. 1992, 63, 271 277. Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. Synthesis of tungsten vinyl alkylidene complexes via the reactions of WCl2(NAr)(PX3)3 (XR, OMe) precursors with 3,3-disubstituted cyclopropenes. J. Am. Chem. Soc. 1993, 8130 8145. Johnson, L. K.; Frey, M.; Ulibarri, T. A.; Virgil, S. C.; Grubbs, R. H.; Ziller, J. W. Alkylidene transfer from phosphoranes to tungsten(IV) imido complexes. J. Am. Chem. Soc. 1993, 8167 8177. Wu, Z.; Benedicto, A. D.; Grubbs, R. H. The living ringopening metathesis polymerization of bicyclo[3.2.0]-heptene catalyzed by a ruthenium alkylidene complex. Macromolecules 1993, 26, 4975 4977. Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. Catalytic ring-closing metathesis of functionalized dienes by a ruthenium carbene complex. J. Am. Chem. Soc. 1993, 115, 9856 9857. Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. Syntheses and activities of new single-component, ruthenium-based olen metathesis catalysts. J. Am. Chem. Soc. 1993 , 115 , 9858 9859. Pu, L.; Grubbs, R. H. New syntheses of benzobarrelenes. J. Org. Chem. 1994, 59, 1351 1353. Benedicto, A. D.; Claverie, J. P.; Grubbs, R. H. On the molecular weight distribution of living polymerization involving chain-transfer agents: computational results, analytical solutions, and experimental investigations using ring-opening metathesis polymerization. Macromolecules 1995, 28(2), 500 511.

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carboxyl groups: living ring opening metathesis polymerization (ROMP) of 2,4-dicarboxy barrelenes. Macromolecules 1997, 30, 3978 3985. Weck, M.; Mohr, B.; Maughon, B. R.; Grubbs, R. H. Synthesis of discotic columnar side-chain liquid crystalline polymers by ring-opening metathesis polymerization (ROMP). Macromolecules 1997, 30(21), 6430 6437. Chang, S.; Grubbs, R. H. A simple method to polydroxylated olen molecules using ring-closing olen metathesis. Tetrahedron Lett. 1997, 38(27), 4757 4760. Wilhelm, T. E.; Belderrain, T. R.; Brown, S. N.; Grubbs, R. H. Reactivity of Ru(H)(H2)Cl(PCy3)2 with propargyl and vinyl chlorides: new methodology to give metathesis-active ruthenium carbenes. Organometallics 1997 , 16(18), 3867 3869. Belderrain, T. R.; Grubbs, R. H. Reaction between Ru(0) or Ru(0) precursor complexes and dihalocompounds. A new method for the synthesis of ruthenium olen metathesis catalysts. Organometallics 1997, 16(18), 4001 4003. Lynn, D. M.; Mohr, B.; Grubbs, R. H. Living ring-opening metathesis polymerization in water. J. Am. Chem. Soc. 1998, 120, 1627 1628. Kirkland, T. A.; Grubbs, R. H. The effects of olen substitution on the ring-closing metathesis of dienes. J. Org. Chem. 1997, 62(21), 73107318. Wagaman, M. W.; Bellmann, E.; Cucullu, M.; Grubbs, R. H. Synthesis of substituted bicyclo[2.2.2]octatrienes. J. Org. Chem. 1997, 62(26), 9076 9082. Zuercher, W. J.; Scholl, M.; Grubbs, R. H. Rutheniumcatalyzed polycyclization reactions. J. Org. Chem. 1998, 63(13), 4291 4298. Grubbs, R. H.; Lynn, D. M. Olen metathesis. In Aqueous Phase Organometallic Catalysis; Cornils, B., Herrmann, W. A., Eds.; VCH: Weinheim, 1998; pp 466 476. Chang, S.; Grubbs, R. H. A highly efcient and practical synthesis of chromene derivatives using ring-closing olen metathesis. J. Org. Chem. 1998, 63(3), 864 866. Nolan, S. P.; Belderrain, T. R.; Grubbs, R. H. Convenient synthesis of ruthenium (II) dihydride phosphine complexes H2Ru(PP)2 and H2Ru(PR3)x (x3 and 4). Organometallics 1997, 16, 5569 5571. Morehead, Jr. A.; Grubbs, R. Formation of bridged bicycloalkenes via ring closing metathesis. Chem. Commun. 1998, 275276. Grubbs, R. H.; Chang, S. Recent advances in olen metathesis and its application in organic synthesis. Tetrahedron 1998, 54, 4413 4450. Dias, E. L.; Grubbs, R. H. Synthesis and investigation of homo- and heterobimetallic ruthenium olen metathesis catalysts exhibiting increased activities. Organometallics 1998, 17(13), 2758 2767. Chang, S.; Jones, II., L.; Wang, C.; Henling, L. M.; Grubbs, R. H. Synthesis and characterization of new ruthenium-based olen metathesis catalysts coordinated with Bidentate Schiff base ligands. Organometallics 1998, 17(16), 3460 3465. OLeary, D. J.; Miller, S. J.; Grubbs, R. H. Templatepromoted dimerization of C-allylglycine: a convenient synthesis of (S,S)-2,7-diaminosuberic acid. Tetrahedron Lett. 1998, 39(13), 1628 1689. Ulman, M.; Grubbs, R. H. Relative reaction rates of olen substrates with ruthenium (II) carbene metathesis initiators. Organometallics 1998, 17(12), 2484 2489. Bellmann, E.; Shaheen, S. E.; Thayumanavan, S.; Grubbs,

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R. H.; Marder, S. R.; Kippelen, B.; Peyghambarian, N. New triarylamine containing polymers as hole transport materials in organic light emitting diodes: effect of polymer structure and crosslinking on device characteristics. Chem. Mater. 1998, 10(6), 1668 1676. Cucullu, M. E.; Nolan, S. P.; Belderrain, T. R.; Grubbs, R. H. Catalytic dehalogenation of aryl chlorides mediated by ruthenium(II) phosphine complexes. Organometallics 1999, 18, 1299 1304. Wang, C.; Friedrich, S.; Li, R. T.; Grubbs, R. H.; Bansleben, D. A.; Day, M. W. Neutral Ni(II) based catalysts for ethylene polymerization. Organometallics 1998, 17(15), 3149 3151. Coates, G. W.; Dunn, A. R.; Henling, L. M.; Ziller, J. W.; Lobkovsky, E. B.; Grubbs, R. H. Phenyl-peruorophenyl stacking interactions: topochemical [22] photodimerization and photopolymerization of olenic compounds. J. Am. Chem. Soc. 1998, 120(15), 3641 3649. Doleman, B. J.; Sanner, R. D.; Severin, E. J.; Grubbs, R. H.; Lewis, N. S. Use of compatible polymer blends to fabricate arrays of carbon black-polymer composite vapor detectors. Anal. Chem. 1998, 70, 2560 2564. Blackwell, H. E.; Grubbs, R. H. Highly efcient synthesis of covalently cross-linked peptide helices by ring-closing metathesis. Angew. Chem., Int. Ed. 1998 , 37 (23), 3281 3284. Cucullu, M. E.; Nolan, S. P.; Belderrain, T. R.; Grubbs, R. H. Catalytic dehalogenation of aryl chlorides mediated by ruthenium (II) phosphine complexes. Organometallics 1999, 18, 1299 1304. Sanford, M. S.; Henling, L. M.; Grubbs, R. H. Synthesis and reactivity of neutral and cationic ruthenium (II) tris(pyrazolyl)borate alkylidenes. Organometallics 1998, 17(24), 5384 5389. Kirkland, T. A.; Lynn, D. M.; Grubbs, R. H. Ring-closing metathesis in methanol and water. J. Org. Chem. 1998, 63(26), 9904 9909. Cucullu, M. E.; Li, C.; Nolan, S. P.; Nguyen, S. T.; Grubbs, R. H. Thermochemical Investigation of Phosphine Ligand Substitution Reactions in trans-(PR3)2Cl2RuvCCvCPh2 Complexes. Organometallics 1998, 17(24), 5565 5568. Grubbs, R. H.; Khosravi, E. Ring-Opening Metathesis Polymerization (ROMP) and Related Processes. In Material Science and Technology, Vol., Schmitt, H., Ed., Wiley-VCH: Weinheim. Bellmann, E.; Shaheen, S. E.; Grubbs, R. H.; Marder, S. R.; Kippelen, B.; Peyghambarian, N. Organic two-layer lightemitting diodes based on high Tg hole-transporting polymers with different redox potentials. Chem. Mater. 1999, 11, 399 407. Weck, M.; Jackiw, J. J.; Rossi, R. R.; Weiss, P. S.; Grubbs, R. H. Ring-opening metathesis polymerization from surfaces. J. Am. Chem. Soc. 1999, 121(16), 4088 4089. OLeary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. A new method for cross-metathesis of terminal olens. Tetrahedron Lett. 1998, 39, 7427 7430. OLeary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Miura, K.; Grubbs, R. H. Terminal olen cross-metathesis with acrolein acetals. Tetrahedron Lett. 1999 , 40 , 1091 1094. Scholl, M.; Grubbs, R. H. Total Synthesis of (2) and (^)-frontalin via ring-closing metathesis. Tetrahedron Lett. 1999, 40, 1425 1428. Matzger, A. J.; Lawrence, C. E.; Grubbs, R. H.; Lewis, N. S.

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Combination approaches to the synthesis of vapor detector arrays for use in an electronic nose. J. Comb. Chem. 2000, 2, 301 304. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Increased ring closing metathesis activity of ruthenium-based olen metathesis catalysts coordinated with imidazolin-2ylidene ligands. Tetrahedron Lett. 1999, 40, 2247 2250. Weck, M.; Dunn, A. R.; Matsumoto, K.; Grubbs, R. H. Inuence of peruoroarenearene interactions on the phase behavior of liquid crystalline and polymeric materials. Angew. Chem., Int. Ed. Engl. 1999, 38, 2741 2745. Ulman, M.; Grubbs, R. H. Ruthenium carbene-based olen metathesis initiators: catalyst decomposition and longevity. J. Org. Chem. 1999, 64(19), 7202 7207. Weck, M.; Mohr, B.; Sauvage, J-P.; Grubbs, R. H. Synthesis of catenane structures via ring-closing metathesis. J. Org. Chem. 1999, 64(15), 5463 5471. Maynard, H. D.; Grubbs, R. H. Purication technique for the removal of ruthenium from olen metathesis reaction products. Tetrahedron Lett. 1999, 40, 4137 4140. Bielawski, C. W.; Morita, T.; Grubbs, R. H. Synthesis of ABA triblock copolymers via a tandem ring-opening metathesis polymerization (ROMP)atom transfer radical polymerization (ATRP) approach. Macromolecules 2000, 33(3), 678 680. Maughon, B. R.; Morita, T.; Bielawski, C. W.; Grubbs, R. H. Synthesis of cross-linking of telechelic poly(butadiene)s derived from ring-opening metathesis polymerization. Macromolecules 2000, 33(6), 1929 1935. Maynard, H. D.; Grubbs, R. H. Synthesis of functionalized polyethers by ring-opening metathesis polymerization of unsaturated crown ethers. Macromolecules 1999, 33(21), 6917 6924. Sotzing, G. A.; Bringlin, S. M.; Grubbs, R. H.; Lewis, N. S. Preparation and properties of vapor detector arrays formed from poly(3,4-ethylenedioxy)thiophene-poly(styrene sulfonate)/insulating polymer composites. Anal. Chem. 2000, 3181 3190. Shaheen, S. E.; Jabbour, G. E.; Kippelen, B.; Peyghambarian, N.; Anderson, J. D.; Marder, S. R.; Armstrong, N. R.; Bellmann, E.; Grubbs, R. H. Organic light-emitting diode with 20 lm/W efciency using a triphenyldiamine side-group polymer as the hole transport layer. Appl. Phys. Lett. 1999, 74(21), 3212 3214. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Synthesis and activity of a new generation of ruthenium-based olen metathesis catalysts coordinated with 1,3-dimesityl-4,5dihydro-imidazol-2-ylidene ligands. Org. Lett. 1999, 1(6), 953 956. Blackwell, H. E.; OLeary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. New approaches to olen cross-metathesis. J. Am. Chem. Soc. 2000, 122, 58 71. Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friedrich, S. K.; Grubbs, R. H.; Bansleben, D. A. Neutral single component nickel (II) catalysts that tolerate heteroatoms. Science 2000, 287, 460 462. Habbour, G. E.; Shalheen, S. E.; Morrell, M. M.; Anderson, J. D.; Lee, P.; Thayumanavan, S.; Barlow, S.; Bellmann, E.; Grubbs, R. H.; Kippelen, B.; Marder, S.; Armstrong, N. R.; Peyghambarian, N. High Tg hole transport polymers for the fabrication of bright and efcient organic light-emitting

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devices with an air-stable cathode. IEEE J. Quant. Electron. 2000, 36, 12 17. Sotzing, G. A.; Phend, J. N.; Grubbs, R. H.; Lewis, N. S. Highly sensitive detection and discrimination of biogenic amines utilizing arrays of polyaniline/carbon black composite vapor detectors. Chem. Mater. 2000, 12, 593 595. Bellmann, E.; Jabbour, G. E.; Grubbs, R. H.; Peyghambarian, N. Hole transport polymers with improved interfacial contact to the anode material. Chem. Mater. 2000, 12, 1349 1353. Chatterjee, A. K.; Grubbs, R. H. Synthesis of trisubstituted alkenes via olen cross-metathesis. Org. Lett. 1999, 1(11), 1751 1753. Morita, T.; Maughon, B. R.; Bielawski, C. W.; Grubbs, R. H. A ring-opening polymerization (ROMP) approach to carboxyl and amino terminated telechelic poly(butadiens)s. Macromolecules 2000, 33, 6621 6623. Lynn, D. M.; Mohr, B.; Grubbs, R. H.; Henling, L. M.; Day, M. W. Water-soluble ruthenium alkylidenes: synthesis, characterization, and application to olen metathesis in protic solvents. J. Am. Chem. Soc. 2000 , 122 (28), 6601 6609. Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. Synthesis of functionalized olens via cross and ring-closing metatheses. J. Am. Chem. Soc. 2000, 122(15), 3783 3784. Bielawski, C. W.; Grubbs, R. H. Highly efcient ringopening metathesis polymerization (ROMP) using new ruthenium catalysts containing N-heterocyclic carbene ligands. Angew. Chem., Int. Ed. Engl. 2000, 39(16), 2903 2906, Angew. Chem. 2000, 112 (16), 30253028. Maynard, H. D.; Okada, S. Y.; Grubbs, R. H. Synthesis of norbornenyl polymers with bioactive oligopeptides by ringopening metathesis polymerization. Macromolecules 2000, 33(17), 6239 6248. Ulman, M.; Belderrain, T. R.; Grubbs, R. H. A series of ruthenium(II) ester-carbene complexes as olen metathesis initiators: metathesis of acrylates. Tetrahedron Lett. 2000, 41, 4689 4693. Bielawski, C. W.; Scherman, O. A.; Grubbs, R. H. Highly efcient syntheses of acetoxy and hydroxy terminated telechelic poly(butadiene)s using ruthenium catalysts containing N-heterocyclic ligands. Polymer 2001, 42, 4939 4945. Louie, J.; Grubbs, R. H. Highly active iron imidazolydidene catalysts for atom transfer radical polymerization. Chem. Commun. 2000, 1479 1480. Bielawski, C. W.; Louie, J.; Grubbs, R. H. Tandem catalysis: ring-opening metathesis polymerization (ROMP), atom transfer radical polymerization (ATRP), and hydrogenation using a single ruthenium complex. J. Am. Chem. Soc. 2000, 122(51), 12872 12873. Sanford, M. S.; Henling, L. M.; Day, M. W.; Grubbs, R. H. Ruthenium-based four coordinate olen metathesis catalysts. Angew. Chem., Int. Ed. 2000, 39(19), 3451 3453, Angew. Chem. 2000, 112 (19), 3593 3595. Lynn, D. M.; Grubbs, R. H. Novel reactivity of ruthenium alkylidenes in protic solvents: degenerate alkylidene proton exchange. J. Am. Chem. Soc. Commun. 2001, 123(14), 3187 3193. Lee, C. W.; Grubbs, R. H. Stereoselectivity of macrocyclic ring-closing olen metathesis. Org. Lett. 2000, 2(14), 2145 2147. Trnka, T.; Grubbs, R. H. The development of L2X2RuCHR

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olen metathesis catalysts: an organometallic success story. Acc. Chem. Res. 2001, (34), 18 29. Bing, R. J.; Yamamoto, T.; Kim, H.; Grubbs, R. H. The pharmacology of a new nitric oxide donor: B-NOD. Biochem. Biophys. Res. Commun. 2000, 275, 350 353. Matzger, A. J.; Henling, L. M.; Grubbs, R. H. The crystal structures of 1,3,5-tris(phenylethynyl)benzene with its pentadecauoro derivative and with octauoronaphthalene: the inuence of multiple arene-peruoroarene interactions. Chem. Commun. Submitted for publication. Louie, J.; Grubbs, R. H. Reaction of diazoalkanes with iron phosphine complexes affords novel phosphazine complexes. Organometallics 2001, 20, 481 484. Morgan, J. P.; Grubbs, R. H. In situ preparation of a highly active N-heterocyclic carbene-coordinated olen metathesis catalyst. Org. Lett. 2000, 2(20), 3153 3155. Louie, J.; Grubbs, R. H. Highly active metathesis catalysts generated in situ from inexpensive and air stable precursors. Angew. Chem., Int. Ed. Engl. 2001, 40, 247 249, Angew. Chem. 2001, 113 (1), 253 255. Maynard, H. D.; Okada, S. Y.; Grubbs, R. H. Inhibition of cell adhesion to bronectin by oligopeptide substituted polynorbornenes. J. Am. Chem. Soc. 2001, 123, 1275 1279. Sanford, M. S.; Ulman, M.; Grubbs, R. H. New insights into the mechanism of ruthenium catalyzed olen metathesis reactions. J. Am. Chem. Soc. 2001, 123, 749 750. Choi, T-L.; Chatterjee, A. K.; Grubbs, R. H. Synthesis of a, b-unsaturated amides by olen cross-metathesis. Angew. Chem., Int. Ed. Engl. 2001, 40(7), 1277 1279, Angew. Chem. 2001, 113 (7), 1317 1319. Lee, C. W.; Grubbs, R. H. Formation of macrocycles via ring-closing olen metathesis. A succinct synthesis of (2)-pyrenophorin. J. Am. Chem. Soc. Submitted for publication. Scherman, O. A.; Grubbs, R. H. Polycyclooctatetraene (polyacetylene) produced with a ruthenium olen metathesis catalyst. Synth. Met. 2001, 124, 431 434. Juang, A.; Scherman, O. A.; Grubbs, R. H.; Lewis, N. S. Formation of covalently attached polymer overlayers on Si(111) surfaces using ring-opening metathesis polymerization methods. Langmuir 2001, 17, 1321 1323. Blackwell, H. E.; Sadowsky, J. D.; Howard, R. J.; Sampson, J. N.; Chao, J. A.; Steinmetz, W. E.; OLeary, D. J.; Grubbs, R. H. Ring-closing metathesis of olenic peptides: design, synthesis, and structural characterization of macrocyclic helical peptides. J. Org. Chem. 2001, 66(16), 5291 5302. Sanford, M. S.; Love, J. A.; Grubbs, R. H. Mechanism and activity of ruthenium olen metathesis catalysts. J. Am. Chem. Soc. 2001, 123, 6543 6554. Trnka, T. M.; Henling, L. M.; Day, M. W.; Grubbs, R. H. Novel h3-vinylcarbene complexes derived from rutheniumbased olen metathesis catalysts. Organometallics 2001, 20, 3845 3847. Chatterjee, A. K.; Choi, T-L.; Grubbs, R. H. Synthesis of vinyl and allyphosphonates by olen cross-metathesis. Synlett 2001, SI, 1034 1037. Bielawski, C. W.; Benitez, D.; Morita, T.; Grubbs, R. H. Synthesis of end-functionalized poly(norbornene)s via ring-opening metathesis polymerization (ROMP). Macromolecules 2001, 34(25), 8610 8618. Choi, T.-L.; Lee, C. W.; Chatterjee, A. K.; Grubbs, R. H. Olen metathesis involving ruthenium enoic carbene complexes. J. Am. Chem. Soc. 2001, 123(42), 10417 10418.

353. Lee, C. W.; Grubbs, R. H. Formation of macrocycles via ring-closing olen metathesis. J. Org. Chem. 2001, 66(21), 5158 7155. 354. Sanford, M. S.; Valdez, M. R.; Grubbs, R. H. Reaction of Tp(PPh3)Ru((2-O2CCHPh2) with carbene and vinylidene precursors. Organometallics 2001, 20(25), 5455 5463. 355. Sanford, M. S.; Love, J. A.; Grubbs, R. H. A versatile precursor for the synthesis of new ruthenium olen metathesis catalysts. Organometallics 2001, 20(25), 5314 5318. 356. Bielawski, C.; Grubbs, R. H. Increasing the initiation efciency of ruthenium based ring-opening metathesis polymerization (ROMP) initiators: the effect of excess phosphine. Macromolecules 2001, 64(26), 8838 8840. 357. Trnka, T. M.; Day, M. W.; Grubbs, R. H. Olen metathesis with 1,1-diuoroethylene. Angew. Chem., Int. Ed. Engl. 2001, 40, 3441 3444. 358. Louie, J.; Bielawski, C. W.; Grubbs, R. H. Tandem catalysis: the sequential mediation of olen metathesis, hydrogenation, and hydrogen transfer using single component ruthenium complexes. J. Am. Chem. Soc. 2001, 123, 11312 11313. 359. Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Enantioselective ruthenium-catalyzed ring-closing metathesis. Org. Lett. 2001, 3(20), 3225 3228. 360. Schwartz, D. M.; Jethmalani, J. M.; Sandstedt, C. A.; Korneld, J. A.; Grubbs, R. H. Post implantation adjustable intraocular lenses. No. 2. Ophthalmology clinics of north america: refractive surgery; McLeod, S. D., McDonnell, P. J., Eds.; W.B. Saunders: Philadelphia, 2001; Vol. 14, pp 339 345. 361. Morgan, J. P.; Morrill, C.; Grubbs, R. H. Selective ring opening cross metathesis of cyclooctadiene and trisubstituted cycloolens. Org. Lett. 2002, 4(1), 67 70. 362. Choi, T.-L.; Grubbs, R. H. Tandem ring-closing metathesis reaction with ruthenium catalyst containing N-heterocyclic ligand. Chem. Commun. 2001, 2648 2649. 363. Goldberg, S. D.; Grubbs, R. H. A one-pot cross-metathesis/ allylboration reaction; a three component coupling for the synthesis of functionalized homoallylic alcohols. Angew. Chem., Int. Ed. Engl. 2002, 41(5), 807 810, Angew. Chem. 2002, 114 (5), 835 838. 364. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Hwang, S.; Grubbs, R. H.; Roberts, W. P.; Litzau, J. J. Linear functionalized polyethylene prepared with single component, neutral Ni(II) complexes. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 2842 2854. 365. Scherman, O. A.; Kim, H. M.; Grubbs, R. H. Synthesis of well-dened poly(vinylalcohol2-alt-methylene) via ring opening metathesis polymerization (ROMP). Macromolecules 2002, 35(14), 5366 5371. 366. Toste, F. D.; Chatterjee, A. K.; Grubbs, R. H. Functional group diversity by ruthenium catalyzed olen cross-metathesis. Pure Appl. Chem. 2002, 74(1), 7 10. 367. Louie, J.; Grubbs, R. H. Metathesis of electron rich olens: structure and reactivity of electron rich carbene complexes. Organometallics 2002, 21(11), 2153 2164. 368. Grubbs, R. H.; Trnka, T. M.; Sanford, M. S. Transition metalcarbene complexes in olen metathesis and related reactions. In Fundamentals of Molecular Catalysis; Yamamoto, A.; Kurosawa, H. Eds.; Elsevier: Amsterdam, Submitted for publication. 369. Koscho, M. E.; Grubbs, R. H.; Lewis, N. S. Properties of vapor detector arrays formed through plasticization of carbon

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black-organic polymer composites. Anal. Chem. 2002, 74(6), 1307 1315. Kilbinger, A. F. M.; Grubbs, R. H. Arene-peruoroarene interactions as physical cross-links for hydrogel formation. Angew. Chem., Int. Ed. Engl 2002, 41(9), 1563 1566, Angew. Chem. 2002, 114 (9), 1633 1636. Grubbs, R. H. Cross metathesis of functionalized olens. Chimia 2002, 56(1 2), 21. Lee, C. W.; Choi, T-L.; Grubbs, R. H. Ring expansion via olen metathesis. J. Am. Chem. Soc. 2002, 124(13), 3224 3225. Chatterjee, A. K.; Grubbs, R. H. Formal vinyl C H activation and allylic oxidation by olen metathesis. Angew. Chem., Int. Ed. Engl 2002, 41(17), 3171 3174, Angew. Chem. 2002, 114 (17), 3303 3306. Chatterjee, A. K.; Toste, F. D.; Choi, T-L.; Grubbs, R. H. Ruthenium-catalyzed olen cross metathesis of styrenes as an alternative to the heck and cross-coupling reactions. Adv. Synth. Catal. 2002, 344(67), 634 637. Chatterjee, A. K.; Sanders, D. P.; Grubbs, R. H. Synthesis of symmetrical trisubstituted olens by cross metathesis. Org. Lett. 2002, 4(11), 1939 1942. Grubbs, R. H.; Sanford, M. Mechanism of ruthenium based olen metathesis catalysts. In Ring Opening Metathesis Polymerisation and Related Chemistry; Khosravi, E., Szymanska-Buzar, T., Eds.; Kluwer: The Netherlands, 2002; pp 17 21. Ferguson, M. L.; OLeary, D. J.; Grubbs, R. H. Ring-closing metathesis synthesis of N-Boc-3-pyrroline. Org. Synth. 2003, 80, 85 92. Rolle, T.; Grubbs, R. H. Ring closing metathesis in protic media by means of a neutral and polar ruthenium benzylidene complex. Chem. Commun. 2002, 10, 1070 1071. Rutenberg, I.; Choi, T. L.; Grubbs, R. H. Synthesis of A,Balternating copolymers by ring opening insertion metathesis polymerization. Angew. Chem., Int. Ed. Engl 2002, 41(20), 3839 3841. Kahnberg, P.; Lee, C. W.; Grubbs, R. H.; Sterner, O. Alternative routes to pterulone. Tetrahedron 2002, 58(26), 5203 5208. Tran, H. V.; Hung, R. J.; Chiba, T.; Yamada, S.; Mrozek, T.; Hsieh, Y-T.; Chambers, C. R.; Osborn, B. P.; Trinque, B. C.; Pinnow, M. J.; MacDonald, S. A.; Willson, C. G.; Sanders, D. P.; Connor, E. R.; Grubbs, R. H.; Conley, W. Metalcatalyzed addition polymers for 157 nm resist applications: 2. Fluorinated norbornenes: synthesis, polymerization, and initial imaging results. Macromolecules 2002, 35(17), 6539 6549. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. An endless route to cyclic polymers. Science 2002, 297, 2041 2044. Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. A practical and highly active ruthenium-based catalyst that effects cross metathesis of acrylonitrile. Angew. Chem., Int. Ed. Engl. 2002, 41(21), 4035 4037. Trnka, T. M.; Morgan, J. P.; Sanford, M. S.; Wilhelm, T. E.; Scholl, M.; Choi, T-L.; Ding, S.; Day, M. W.; Grubbs, R. H. Synthesis and activity of ruthenium alkylidene complexes coordinated with phosphine and N-heterocyclic carbene ligands. J. Am. Chem. Soc. 2003, 125(9), 2546 2558. Chatterjee, A. K.; Toste, F. D.; Goldberg, S. D.; Grubbs, R. H. Synthesis of coumarins by ring-closing metathesis. Pure Appl. Chem. 2003, 75(4), 421 425. Hejl, A.; Trnka, T. M.; Day, M. W.; Grubbs, R. H. Terminal

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ruthenium carbido complexes as (-donor ligands. Chem. Commun. 2002, 2524 2525. Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. Synthesis, structure, and activity of enhanced initiators for olen metathesis reactions. J. Am. Chem. Soc. 2003, 125, 10103 10109. Tillman, E. S.; Koscho, M. E.; Grubbs, R. H.; Lewis, N. S. Enhanced sensitivity to and classication of volatile carboxylic acids using arrays of linear poly(ethylenimine)carbon black composite vapor detectors. Anal. Chem. 2003, 75(7), 1748 1753. Choi, T.-L.; Grubbs, R. H. Controlled living ring-opening metathesis polymerization by fast initiating ruthenium catalyst. Angew. Chem., Int. Ed. Engl. 2003, 42, 17431746. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Waltman, A.; Henling, L.; Grubbs, R. H. Revealing the role of ligand steric bulk in neutral nickel salicylaldamine polyethylene catalysts. J. Am. Chem. Soc. Submitted for publication.. Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. A general model for selectivity in olen cross metathesis. J. Am. Chem. Soc. 2003, 125, 11360 11370. Bielawski, C. W.; Jethmalani, J. M.; Grubbs, R. H. Synthesis of telechelic polyacrylates with unsaturated end-groups. Polymers 2003, 44, 3721 3726. Sanders, D. P.; Connor, E. F.; Grubbs, R. H.; Hung, R. J.; Osborn, B. P.; Chiba, T.; MacDonald, S. A.; Willson, C. G.; Conley, W. Metal-catalyzed addition polymers for 157 nm resist applications: synthesis and polymerization of partially uorinated, ester-functionalized tricyclo[4.2.02,5]non-7-enes. Macromolecules 2003, 36(5), 1534 1542. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Synthesis of cyclic polybutadiene via ring-opening metathesis polymerization: the importance of removing trace linear contaminants. J. Am. Chem. Soc. 2003, 125(28), 8424 8425. Kilbinger, A. F. M.; Cantrill, S. J.; Waltman, A. W.; Day, M. W.; Grubbs, R. H. Magic ring rotaxanes via olen metathesis. Angew. Chem., Int. Ed. Engl. 2003, 42 , 3281 3285. Scherman, O. A.; Rutenberg, I. M.; Grubbs, R. H. Direct synthesis of soluble, end-functionalized polyenes and polyacetylene block-copolymers. J. Am. Chem. Soc. 2003, 125(28), 8515 8522. Morrill, C.; Grubbs, R. H. Synthesis of functionalized vinyl boronates via ruthenium-catalyzed olen cross-metathesis and subsequent conversion to vinyl halides. J. Org. Chem. 2003, 68, 6031 6034. Rutenberg, I. M.; Scherman, O. A.; Bao, Z.; Grubbs, R. H.; Jiang, W. Garfunkel, E. Synthesis of polymer dielectric layers for organic thin lm transistors via surface-initiated ROMP. J. Am. Chem. Soc. Submitted for publication. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Waltman, A. Henling, L.; Grubbs, R. H. Neutral nickel salicylaldamine polyethylene catalysts: the role of ligand steric bulk. Chem. Commun. in press. Trinque, B. C.; Chambers, C. R.; Osborn, B. P.; Callahan, R. P.; Lee, G. S.; Kusumoto, S.; Sanders, D. P.; Grubbs, R. H.; Conley, W. E.; Willson, C. G. Vacuum-UV inuenced design of polymers and dissolution inhibitors for next generation lithography. J. Fluorine Chem. 2003, 122, 17. Trnka, T. M.; Dias, E. L.; Day, M. W.; Grubbs, R. H. Ruthenium alkylidene complexes coordinated with tricylcohexylphosphine and heterocyclic N-donor ligands. ARKIVOC 2002, 28 41, Part 13.

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402. Schwartz, D.; Sandstedt, C.; Chang, S.; Korneld, J.; Jethamalani, J.; Mamalis, N.; Grubbs, R. Materials for remote manipulation in the body: light adjustable intraocular lens. Nature, Submitted for publication. 403. Benitez, D.; Bielawski, C. W.; Grubbs, R. H. A ring-opening metathesis polymerization (ROMP) approach to cyclic polyoctenamers. Macromolecules, Submitted for publication. 404. Yun, J. -S.; Marinez, E. R.; Grubbs, R. H. New rutheniumbased olen metathesis catalyst coordinated with 1,3-dimesityl-1,4,5,6-tetrahydropyrimidin-2-ylidene: synthesis, X-ray structure and reactivity. Organometallics, Submitted for publication.

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Unrefereed Publications
17. 1. Grubbs, R. H.; Hillmyer, M.; Benedicto, A.; Wu, Z. Ringopening metathesis polymerization catalysts. Polym. Prepr. 1994, 35, 688. 2. Chen, Z.; Korneld, J. A.; Claverie, J. P.; Grubbs, R. H. Ringchain equilibria in ring-opening metathesis polymerization (ROMP) of cycloolens. Polym. Prepr. 1994, 35, 692693. 3. Tritto, I.; Sacchi, M. C.; Grubbs, R. H. From ROMP to Ziegler Natta polymerization: a study for obtaining polynorbornene-polyethylene block copolymers. Polym. Prepr. 1994, 35, 696 697. 4. Grubbs, R. H. Transition metal catalyzed reactions of olens in water: olen metathesis and isomerization. In Aqueous th, I. T., Joo , Organometallic Chemistry and Catalysis; Horva F., Eds.; Kluwer: The Netherlands, 1995; pp 15 22. 5. Hillmyer, M. A.; Grubbs, R. H. The ROMP of COD by a well-dened metathesis catalyst in the presence of a difunctional chain transfer agent: the preparation of hydroxy-telechelic 1,4-poly(butadiene). Polym. Prepr. 1993, 34, 388 389. 6. Rock, M. M.; Jozeak, T. H.; Grubbs, R. H. The design and synthesis of electroactive polymers. Polym. Prepr. 1993, 34, 358 359. 7. Bendicto, A. D.; Claverie, J. P.; Grubbs, R. H. Molecular weight of chain-transferred polymers in living polymerizations: comparison between experiment and theory. Polym. Prepr. 1995, 36, 172 173. 8. Fraser, C.; Hillmyer, M.; Gutierrez, E.; Grubbs, R. H. Degradable cyclooctadiene/acetal copolymers: precursors to 1,4-hydroxytelechelic polybutadiene. Polym. Prepr. 1995, 36, 237 238. 9. Wege, V. U.; Grubbs, R. H. Polymer synthesis in conned environmentsmicroemulsion polymerization in monomolecular dendrimeric systems. Polym. Prepr. 1995, 36, 239 240. 10. Grubbs, R. H.; Hillmyer, M.; Li, R.; Diaz, E.; Nguyen, S. T. Ring opening metathesis polymerization catalysts. Macromol. Symp. 1995, 98, 43. 11. Weck, M.; Maughon, B. R.; Mohr, B.; Grubbs, R. H. Inuence of backbone rigidity on the thermotropic behavior of side-chain liquid crystalline (SCLC) polymers synthesized by ring opening metathesis polymerization (ROMP). Polym. Prepr. 1996, 37(1), 587588. 12. Maughon, B. R.; Grubbs, R. H. Synthesis and characterization of crosslinkable polymers through ring opening metathesis polymerization of cyclooctene-5-methacrylate and cyclooctadiene. Polym. Prepr. 1995, 36, 471 472. 13. Leising, G.; Kopping-Grem, G.; Meghdadi, F.; Niko, A.;

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Tasch, S.; Fischer, W.; Pu, L.; Wagaman, M. W.; Grubbs, R. H.; et al. Electroluminescence and photoluminescence of conjugated polymers and oligomers. Prod. SPIE-Int. Soc. Opt. Eng. 1995, 307 314. Morita, T.; Maughon, B. R.; Grubbs, R. H. Synthesis of cross-linkable telechelic poly(butadiene) via ring-opening metathesis polymerization. Polym. Prepr. 1998 , 39 , 226 227, Abs. Pap. ACS 1998, 215, 231. Lynn, D. M.; Mohr, B.; Grubbs, R. H. Living ring-opening metathesis polymerization in water via activation of watersoluble ruthenium alkylidenes. Polym. Prepr. 1998, 39, 278 279, Abs. Pap. ACS 1998, 215, 52. Grubbs, R. H.; Blackwell, H.; Maughon, B.; Dias, E. Synthesis of organic molecules and materials using ruthenium carbene. Abs. Pap. ACS 1997, 213, 270. Grubbs, R. H.; Bansleben, D. A.; Wang, C. M.; Friedrich, S.; Younkin, T.; et al. The polymerization of ethylene with neutral, late metal catalysts. Abs. Pap. ACS 1998, 215, 37. Kirkland, T. A.; Lynn, D. M.; Grubbs, R. H. Ring-closing metathesis in water and methanol catalyzed by ruthenium alkylidene complexes. Abs. Pap. ACS 1998, 215, 73. Blackwell, H. E.; Grubbs, R. H. Synthesis of constrained cyclic peptide helices by ring closing metathesis. Abs. Pap. ACS 1998, 215, 72. Elder, D. L.; Wagamen, M. W.; Grubbs, R. H. Photoluminescence properties of dialkoxy poly(1,4-napthalenevinylene) (PNV) homopolymers and copolymers synthesized by ROMP-aromatization route. Polym. Prepr. 1998, 39(2), 733 734. Maynard, H. D.; Grubbs, R. H.; Tandem, A. Approach to the synthesis of functionalized polyethers based on ring-closing metathesis and ring-opening metathesis polymerization. Polym. Prepr. 1998, 39(2), 523 524. Bellmann, E.; Shaheen, S. E.; Marder, S. R.; Kippelen, B.; Grubbs, R. H.; Peyghambarian, N. Synthesis of high-Tg holetransporting polymers with different redox potentials and their performance in organic two layer LEDs. SPIE 1998. San Diego, CA. Morita, T.; Maughon, B. R.; Grubbs, R. H. Synthesis of cross-linkable telechelic poly(butadiene) via ring-opening metathesis polymerization. Polym. Prepr. 1998, 39(1), 226 227. Lynn, D. M.; Mohr, B.; Grubbs, R. H. Living ring-opening metathesis polymerization in water via activation of watersoluble ruthenium alkylidenes. Polym. Prepr. 1998, 39(1), 278 279. Lewis, N. S.; Lonergan, M. C.; Severin, E. J.; Doleman, B. J.; Grubbs, R. H. Array-based vapor sensing using chemically sensitive, carbon black-polymer resistors. Proc. SPIEInt. Soc. Opt. Eng. 1997, 3079, 660 670. Fujimura, O.; Javier De La Mata, F.; Grubbs, R. H. Synthesis of new chiral ligands and their group VI metal alkylidene complexes. Chemtracts 1998, 11, 143 144. Ring-opening metathesis polymerization from surfaces. Polym. Mater. Sci. Eng. 1998, 79, 72 73. Jethmalani, J. M.; Korneld, J. A.; Grubbs, R. H.; Schwartz, D. M. Photo-induced refractive index modulation of bismethacrylate endcapped siloxane macromer in poly(dimethylsiloxane) (pdms) matrix. Polym. Prepr. 1999, 40(2), 234 235. Jethmalani, J. M.; Korneld, J. A.; Grubbs, R. H.; Schwartz, D. M. Silicones for photo-induced refractive index modulation: divinyl endcapped /siloxane macromer in

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poly(dimethylsiloxane) matrix. Polym. Prepr. 1999, 40(2), 271 272. Bielawski, C. W.; Grubbs, R. H. Synthesis of ABA triblock copolymers via a tandem ring-opening metathesis polymerization (ROMP)atom transfer radical polymerization (ATRP) approach. Polym. Prepr. 2000, 41(1), 12 13. Kilbinger, A. F. M.; Grubbs, R. H. Physical polymer networks via peruoroarene-arene interactions. Polym. Mater. Sci. Eng. 2001, 85, 350351. Grubbs, R. H. Olen metathesis: a powerful reaction begins to reach its potential. Adv. Synth. Catal. 2002, 344(67), 569. Maynard, H. D.; Grubbs, R. H.; Hubbell, J. H. Peptidesubsituted polymers as synthetic analogs of natural macromolecules. Polym. Mater. Sci. Eng. 2002, 87, 515. Pinnow, M. J.; Noyes, III., B. F.; Tran, H. V.; Tattersall, P. I.; Cho, S.; Klopp, J. M.; Bensel, N.; Frechet, J. M. J.; Sanders, D. P.; Grubbs, R. H.; Willson, C. G. Design and syntheses of

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mass persistent photoresists. Polym. Mater. Sci. Eng. 2002, 87, 403404. Grubbs, R. H. The breadth and depth of olen metathesis chemistry. Polym. Mater. Sci. Eng. 2003, 88, 66. Scherman, O. A.; Walker, R.; Grubbs, R. H. Synthesis of regioregular and stereoregular ethylene vinyl alcohol copolymers via romp of a protected cyclooctene-5,6-(cis and trans)-diol. Polym. Prepr. 2003, 44(1), 952 953. Jordan, J. P.; Scherman, O. A.; Grubbs, R. H. Synthesis of poly(vinylamine) copolymers by the ROMP of temporarily strained cyclic olens. Polym. Prepr. 2003, 44(1), 841 842. Choi, T.-L.; Grubbs, R. H. Controlled living polymerization by fast initiating ruthenium catalyst. Polym. Prepr. 2003, 44(1), 783 784. Rutenberg, I. M.; Scherman, O. A.; Bao, Z.; Grubbs, R. H. Synthesis of polymer dielectric layers via romp for use in organic circuit devices. Polym. Prepr. 2003, 44(1), 566 567.