Festschrift in Honor of IstvÃ¡n T. HorvÃ¡th - ACS Publications - American

Editorial Cite This: ACS Sustainable Chem. Eng. 2018, 6, 9523−9529

Festschrift in Honor of István T. Horváth

ACS Sustainable Chem. Eng. 2018.6:9523-9529. Downloaded from pubs.acs.org by KAOHSIUNG MEDICAL UNIV on 08/08/18. For personal use only.

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am pleased to introduce the Festschrift of ACS Sustainable Chemistry & Engineering that honors István T. Horvátha Chair Professor of Chemistry at the City University of Hong Kong, an Adjunct Professor at Eötvös Loránd University, Budapest, Hungary, and a Honorary Professor at the Budapest University of Technology and Economicson the occasion of his 65th birthday (Figure 1). I do so on behalf of his numerous friends and colleagues, many of whom are represented in the articles that follow. To best accommodate these diverse contributions, the Festschrift has been presented as a virtual special issue (Festschrift in Honor of István T. Horváth).

Figure 2. Cobalt-catalyzed conversion of acetylene and carbon monoxide to trans- and cis-bifurandiones and the formation of the first dinuclear bis(carbene) cobalt complex.

nitrogen was used to condense acetylene in the bottom of a glass ampule of a known weight, which was then sealed by the glassblower József Vladár, generating two parts. The combined masses of the upper part and lower part (containing the acetylene in the form of a white solid) were measured on a balance. The closed lower part, the solvent acetone, and the catalyst precursor, Co2(CO)8, were placed in a stainless steel cylinder of a high pressure reactor. The head of the reactor was secured onto the cylinder, closed, and pressurized with 100 bar of carbon monoxide. After heating and shaking the reactor at 125 °C for 24 h, the reactor was cooled, the gas released, and the contents transferred to a flask. The ampule had vanished and only a dark suspension containing glass microparticles and some white solids remained. The trans- and cis-bifurandione were then isolated by recrystallization and characterized by NMR. It was not uncommon for Horváth to drive overnight to the other end of the country (Szeged) to enlist the assistance of Dr. István Pelczer, a life-long friend and collaborator now at Princeton University, with the NMR characterization. Horváth also studied reactions of related dicobalt lactone complexes (inset, Figure 2) with different acetylenes. The products were best isolated by preparative thin layer chromatography (TLC). He became a master of making 1 mm thick silica TLC plates (25 cm × 25 cm) at the rate of hundreds per week. In particular, the reaction with diiodoacetylene led to the formation of the first dinuclear bis(carbene) complex with two different carbene ligands.3 Horváth was an Assistant Professor at the Department of Chemistry, Veterinary University, Budapest, Hungary (1979− 1981). There he worked on the synthesis of aryl thioamides using the foul smelling Willgerodt−Kindler reaction of aryl aldehydes, sulfur, and methyl bispidine. His next appointment was as a Research Engineer at Chinoin Pharmaceutical and Chemical Works Ltd. in Budapest (1981). In this position, he

Figure 1. István T. Horváth.

István T. Horváth was born in Budapest, Hungary, on August 6, 1953, and grew up in Buda, the hilly side of Budapest. In his childhood, he was a dedicated street-soccer player in the summer and a risk taking street-skier on snowy days in the winter. His love of rock-and-roll began by surreptitiously listening to Radio Free Europe in the 1960s despite the intermittent station jamming. He studied chemistry at the Petrik Lajos Chemical Technical School (Petrik Lajos Vegyipari Technikum) in Budapest between 1967 and 1971, though he mostly focused on team handball. Horváth continued his studies at Veszprém University of Chemical Engineering, Veszprém, Hungary (University of Veszprém from 1991 and the University of Pannonia since 2006). Although his course work was periodically interrupted by his duties as the lead vocalist of a rock-and-roll band, a fourmonth stint as a technician in the Department of Organic Chemistry awakened him to the beauty of organometallic catalysis. He received his Diploma of Chemical Engineering and Ph.D. in Organic Chemistry under the direction of Prof. G. Pályi in 1977 and 1979, respectively. His dissertation involved the mechanism of the cobalt-catalyzed conversion of acetylene and carbon monoxide to trans- and cis-bifurandiones,1 an early example of a reaction with 100% atom economy (Figure 2). One of Horváth’s most memorable experiments involved the measurement of the exact weight of acetylene (HCCH) in a closed ampule.2 A Dewar that had been charged with liquid © 2018 American Chemical Society

Received: July 2, 2018 Published: August 6, 2018 9523

DOI: 10.1021/acssuschemeng.8b03138 ACS Sustainable Chem. Eng. 2018, 6, 9523−9529

ACS Sustainable Chemistry & Engineering

Editorial

Figure 3. Sulfur-assisted cluster condensation of Os3(CO)9(μ3-S)2 with Os3(CO)10(NCMe)2.

participated in separating the components of the macrolide antibiotic primycin4 using chromatography columns packed with TLC silica under low gas pressure. Horváth then switched continents for the first of five times in his career. This brought him to the Department of Chemistry at Yale University in New Haven, Connecticut, where he joined the group of Prof. Richard D. Adams as a Postdoctoral Research Associate (1982−1984). After arriving at New York’s JFK airport on December 28, 1981, his first impressions of North America were shaped by an after-sunset ride on the Connecticut Limousine to New Haven. The journey through snowy small towns of New England, decorated with colorful indoor and outdoor Christmas lighting, resulted in “love at first sight”. The first chemical reaction that he carried out in North America involved the triosmium carbonyl clusters Os3(CO)9(μ3-S)2 and Os3(CO)10(NCMe)2 and yielded the hexaosmium clusters Os6(CO)17(μ4-S)2 and Os6(CO)16(μ3-S)(μ4-S) (Figure 3)..5−7 Because of his experience with preparative TLC, he could easily isolate many different homo- and heteronuclear osmium, platinum, and tungsten sulfido clusters from similar reactions. Single crystals could often be grown, after which Prof. Adams determined the X-ray crystal structures. Adams and Horváth coauthored a remarkable 20 papers in 32 months. Horváth’s stay at Yale left a lasting impression regarding the importance of structure/reactivity relationships. In September of 1984, Horváth returned to Europe, joining the Swiss Federal Institute of Technology in Zürich, Switzerland. He then spent three years as a scientific co-worker with Professors Piero Pino and György Bor. While Pino taught Horváth how to ask hard questions, Bor showed him how to answer by using in situ infrared spectroscopy. Pino and Bor proposed that cobalt−rhodium synergism in catalytic reactions is due to the formation of CoRh(CO)7 from Co2(CO)8 and Rh4(CO)12 under carbon monoxide pressure (Figure 4). Horváth was charged with isolating and characterizing CoRh(CO)7, which had been a “mission impossible” for a number of previous visiting scientists and postdocs. His experiments during the first 2 weeks included the addition of the white pyrophoric solid Na[Co(CO)4], prepared by Dr. Arpad Major, to a precooled n-hexane solution of [Rh(CO)2Cl]2 at −80 °C under carbon monoxide. Surprisingly, the experiments worked, and the very unstable, coordinatively unsaturated CoRh(CO)7 formed, which in turn converted to Co2Rh2(CO)12 upon warming the solution to room temperature under nitrogen.8 Later, it was also discovered that Co2Rh2(CO)12 was in equilibrium with CoRh(CO)7 and CoRh(CO)8 under carbon monoxide pressure at ambient temperature.

Figure 4. Equilibria among cobalt−rhodium clusters under carbon monoxide.

Professors Pino and Bor were kind and flexible enough to allow Horváth to work on some of his own ideas as well. This resulted in his first two independent papers.9,10 The next phase of Horváth’s career took place at the Corporate Research Laboratories of Exxon (now ExxonMobil) Research and Engineering Company in Annandale, New Jersey (1987−1998). Now, he was an independent investigator and became internationally known for developing and applying elegant in situ probes of chemical reactions to attain a molecular level understanding of mechanism. He pioneered the use of in situ NMR and IR monitoring and made significant contributions to the understanding of the mechanisms of many different reactions, especially focusing on those that could be used in developing green processes. These themes have continued in Horváth’s subsequent professional stations at Eötvös Loránd University, Budapest, Hungary (1999−2008), and the City University of Hong Kong (2009-present), where he served as a Department Head for 6 years at each institution. Hence, his research is presented as one continuous narrative for the rest of this article. One of Horváth’s first Exxon studies established that the treatment of lignite with carbon monoxide in water at 315 °C resulted in alkali formate intermediates (HCOO−), which were the active hydride transfer reducing agents.11 New mechanistic insights were reported (frequently in collaboration with 9524



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tions.37 These efforts have spanned decades, from his early days at Exxon through the present. I was lucky to have a ringside seat on the whole story, first as a corporate consultant and later as a collaborator. Chemists had been aware that saturated perfluorocarbons and organic solvents do not generally mix at room temperature. However, fewer knew that these two usually become miscible at elevated temperatures. This gave Horváth the idea of rendering catalysts soluble in saturated perfluorocarbons by adding “perfluorocarbon containing ponytails”, exploiting the principle of “like dissolves like”. This set the stage for his landmark paper with Rábai in Science in 199438 and his follow-up review in Accounts of Chemical Research in 1998,39 which have averaged greater than 48 and 35 citations per year, respectively. These demonstrated how such catalysts could be used in mixtures of saturated fluorocarbon and organic solvents under homogeneous conditions at the high temperature (miscible) limit and recovered in high yields by liquid/liquid phase separation at the low temperature (immiscible) limit (Figure 5).

prominent chemists) for the rhodium-catalyzed hydroformylation of olefins in water,12 ethylene polymerization with cobalt catalysts (with Maurice Brookhart),13 reduction of nitrogencontaining heteroaromatic compounds (with Richard H. Fish),14 conversion of chloroaromatics to saturated hydrocarbons,15 (porphinato)iron-catalyzed isobutane oxidation (with Michael J. Therien),16 alternating copolymerization of propene with CO (with Kyoko Nozaki),17 synthesis of the isotopically labeled insect repellent [1,C-14]N-methylneodecanamide (with Cliff Unkefer),18 Friedel−Crafts acylation in ionic liquids,19 hydromethoxycarbonylation of 1,3-butadiene (with Imre Toth, Ot E. Sielcken, and Stephan Pitter),20,21 cyclooligomerization of isocyanates (with Frank U. Richter),22 oxidative carbonylation of methanol to dimethyl carbonate (with Christian P. Mehnert),23 Beckmann rearrangement of cyclohexanone oxime (with Imre Toth and Ot E. Sielcken),24 acid-catalyzed dehydration of fructose to 5-(hydroxymethyl)-2furaldehyde,25 acid-catalyzed conversion of fructose to γvalerolactone (GVL) in GVL,26 and activation of small molecules including hydrogen (with Carl D. Hoff and Robert H. Crabtree),27 methane,28 and carbon monoxide (with Hans H. Brintzinger and Richard A. Andersen).29 Our own joint in situ IR and NMR investigations of carbon monoxide and methane in super acids resulted in two papers, one describing the first spectroscopic observation of the formyl cation, HCO+, in a condensed phase,30 and the other involving the carbonylation of methane, which remains the most selective reaction of methane today.31 Early on, Horváth recognized the advantages of water as a solvent for catalysis and showed that the dissociation of a water-soluble phosphine ligand from rhodium is controlled not only by the phosphorus−rhodium bond but also by hydrogen bonds between the polar functional groups of neighboring phosphines.12 His work on aqueous systems took place years before water became a pillar of green chemistry. Horváth also co-organized a historically important NATO workshop on “Aqueous Organometallic Chemistry and Catalysis” in Debrecen, Hungary, in 1993one of the first NATO workshops after the collapse of the Eastern Block in Europe.32 Horváth edited a thematic issue of the Journal of Molecular Catalysis on “Catalysis in Water”33 and has reviewed the role of water in catalytic biomass-based technologies to produce chemicals and fuels.34 Horváth has also made key contributions to the understanding of aqueous biphasic catalysis and supported aqueous biphasic catalysis.35 These endeavors sharpened his game with respect to the many subtleties and nuances in multiphase catalysis and its important role in green chemistry. He developed one of the first supported acidic/ionic liquidbased catalytic systems for the facile hydrogenation of aromatics to saturated hydrocarbons.36 Horváth’s investigation of the mechanism of the Beckmann rearrangement of cyclohexanone oxime to caprolactam in oleum24 established that it took place in an ionic liquid medium, which had been heretofore overlooked. The ionic liquid, caprolactamium hydrogen sulfate, has a much lower vapor pressure than oleum due to its strong interaction with sulfur trioxide. This explains why industrial-scale Beckmann rearrangements could be used without any serious accidents and environmental problems for decades. Horváth’s insight regarding biphasic catalysis played a major role in what many regard as his best known and most impactful discovery: fluorous multiphase systems for chemical reac-

Figure 5. Conceptual design: fluorous multiphase systems.

This creative and entirely unforeseen protocol electrified both the catalysis and chemical communities. To emphasize the orthogonal phase properties of saturated fluorocarbons and other common solvents, Horváth coined the term “fluorous”, by analogy to aqueous. Suddenly, there was a “new” phase for chemists to work with, and dozens of researchers jumped into the field.40 Horváth and I obtained a joint grant from the National Science Foundation that funded research at both Exxon and the University of Utah, where my group was then located. My co-workers were always inspired by Horváth’s visits, which featured incisive comments and friendly encouragement. A number of joint papers resulted, involving well-defined fluorous rhodium catalysts, their applications in a host of catalytic reactions,41−43 model mechanistic studies with iridium analogs,44,45 and excursions into C1 chemistry already mentioned above.30,31 Horváth nurtured the field of fluorous chemistry with timely review articles and various independent and collaborative undertakings. Others saw additional applications or extensions, e.g., Dennis P. Curran’s novel methodology for tagging and separating libraries of compounds. Horváth, Curran, and I jointly edited the Handbook of Fluorous Chemistry, which was published in 2004 and remains an essential reference for newcomers to the field.46 A biennial workshop, the International Symposium on Fluorous Technologies (ISoFT), was inaugurated in 2005, for which special thanks are owed to JeanMarc Vincent and Richard Fish.47 The environmental persistence of certain highly fluorinated molecules is now well documented. Horváth has strived to 9525



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Figure 6. Overarching concept: the GVL economy.

Figure 7. Covers of the special issues of Chemical Reviews on environmental chemistry (1995), green chemistry (2007), and sustainable chemistry (2018).

continually refine fluorous protocols to address this and related issues. His recent studies have focused on the use of fluorous ponytails with C1−4-perfluoroalkyl groups, which maintain high fluorophilicity levels but greatly diminish bioaccumulation and any attendant toxicity.48,49 These themes will figure prominently in a review under preparation, tentatively titled Fluorous Chemistry after 25 Years. Another major research thrust in the Horváth group has involved the sustainable conversion of biomass to fuels and chemicals (2003−present). He suggested at the June 2004 International Conference on Renewable Resources and Renewable Energy (Trieste, Italy) that γ-valerolactone (GVL), a naturally occurring chemical and frequently used food additive, could become “the sustainable liquid for energy and chemicals” for future generations.50 GVL occurs in fruits, is nontoxic, and has a high solubility in water, thereby facilitating biodegradation and bioremediation. Its low melting point and high boiling point make it one of the best candidates for a movable liquid in pipes, trucks, and tankers. In addition, it is a safe material for large-scale use due to its low vapor pressure, high flash point, and high stability in air as well as water at neutral pH.51 Horváth has demonstrated that the conversion of carbohydrates to various C5-oxygenates and even to alkanes can be achieved by selecting the proper catalysts and conditions, which could provide a renewable platform for the

chemical industry.52 He has confirmed that GVL can be produced from fructose, glucose, and sucrose, with GVL doing double duty as the green solvent for the process.26,53 He has shown that levulinic acid together with a slight excess of formic acid can be converted to GVL in the presence of a Shvo catalyst with yields greater than 99%. Furthermore, the Shvo catalyst can be recycled several times without any loss of activity.54 The conversion of agricultural residues and paper wastes to GVL, which can also be used as a sustainable lighting and illumination liquid, was recently published.55,56 Other researchers have expanded upon these concepts, all of which lead to very a promising prospectus for the development of a GVL economy (Figure 6). Horváth continues to broaden his range of undertakings in “green chemistry”. He has coauthored a review on the valorization of biomass, which provides a roadmap for the use of biomass-based waste.57 His collaborative work with local restaurants in Hong Kong constituted one of the first experimental demonstrations of converting real food waste to biofuel. He has recently published a new axiom for sustainability: “Nature’s resources, including energy, should be used at a rate at which they can be replaced naturally and the generation of waste cannot be faster than the rate of their remediation”.58 It should be emphasized that this definition is independent from economic, social, and political issues, and 9526



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perhaps more importantly, free of vested or conflicts of interest. In addition, Horváth has introduced the ethanol equivalent or EE,58,59 a novel approach to measure the sustainability of biomass based fuels and carbon chemicals. He has defined EE as “the mass of ethanol needed to deliver the equivalent amount of energy from a given feedstock using energy equivalency or produce the equivalent amount of mass of a carbon-based chemical using molar equivalency”, which was based on first-generation cornbased bioethanol technology as commercially practiced in the United States in 2008. He has shown that the EE can be used as a translational tool between fossil- and biomass-based feedstocks, products, processes, and technologies. Since the EE can be supplied by a given biomass-based technology, the required mass of biomass feedstock, the area of land, and even the volume of water can be calculated. Scenario analyses based on EEs could better visualize the demand of competing technologies on the environment both for experts as well as the general public. Horváth has also defined a sustainability indicator, which can help to assess and compare the sustainability of fossil- and biomass-based chemicals, materials, and fuels.60 As readers may have gathered, Horváth is known for his service and leadership, particularly in the catalysis and green chemistry communities. He has been the editor-in-chief of the Encyclopedia of Catalysis61 and a co-editor of several monographs: Aqueous Organometallic Chemistry and Catalysis,32 Multiphase Homogeneous Catalysis,62 Advanced Green Chemistry,63 and the fluorous reference works already mentioned.46,47 Horváth has served on the editorial boards of numerous journals and has had particularly close ties with Chemical Reviews and Accounts of Chemical Research; for each, he has served as a guest editor of thematic issues dealing with topics such as environmental, green, and sustainable chemistry. A selection of covers for Chemical Reviews is depicted in Figure 7; two of these broke with the long-standing journal tradition of blue backgrounds. Readers are referred to the editorials therein for a number of insightful, provocative, and visionary statements. These include “It is no longer suf f icient to make “marvelous” new molecules solely on the basis of their marketable properties. Although marketability is an appropriate goal, we, as scientists, must also be concerned with our creations’ potentials for environmental impact,”64 and the adaptation of the new axiom of sustainability58 for the definition of “sustainable chemistry”.65 Horváth has played leading roles in the organization of many meetings and symposia, including the U.S. National Science Foundation Organometallic Workshop (for which he and I served as co-chairs, 1991−1993), Gordon Conferences (cochair, organometallic chemistry, 1993, and green chemistry, 2000), the 10th International Symposium on Homogeneous Catalysis (chair, Princeton, 1996), the XVIth FECHEM Conference on Organometallic Chemistry (chair, Budapest, 2005), the sixth Asian-Oceanian Conference on Green and Sustainable Chemistry (chair, Hong Kong, 2016), and ISoFT’11 (chair, Hong Kong, 2011). For the last event, Horváth organized and edited the proceedings into the monograph Fluorous Chemistry.47 Additionally, Horváth was the chairman of the European-wide Cooperation in Science & Technology (COST) program’s COST Action D29 on “Sustainable/Green Chemistry and Chemical Technology” (2002−2007), “one of the most successful actions” according to COST.

Figure 8. Author and the Festschrift honoree relaxing at the Nürnberg Tiergarten (Nuremberg Zoo), 2006.

Horváth’s many accomplishments have been recognized by a variety of awards including the Exxon Golden Tiger Award by Exxon Research & Engineering Company (1991), the inaugural International Fluorous Technologies Award (2005), a Senior Humboldt Research Award (2006), the RSC Green Chemistry Lecture Award (2008), the Hans C. Freeman Lectureship at the University of Sydney (2009), and Honorary Membership in the National Academy of Sciences Literature and Arts of Modena, Italy (2010). He has been named a Fellow of the Royal Society of Chemistry (2013), the American Chemical Society (2014), and the American Association of the Advancement of Science (2016). Horváth has regularly been invited to present lectures at international meetings and conferences, as well as top academic and industrial laboratories worldwide (to date, more than 145 and 220, respectively). Since his return to academia in 1999, Horvath has collaborated with numerous companies (e.g. ExxonMobil, DSM Research, Bayer MaterialScience or Covestro), leading to joint publications and insight into industrial research for his students. Looking back at Horváth’s career, he is among the select group of chemists who have contributed to the start of Green Chemistry, and he is credited for launching entire disciplines based upon seminal papers, i.e., fluorous chemistry38 and the GVL economy.50 Throughout his entire body of work, one is struck by the careful attention to experimental detail, the variety of physical characterization techniques employed, and the careful analysis of data. This is further exemplified in a retrospective by Gábor Náray-Szabó and László T. Mika that is being published concurrently.66 Horváth’s love for chemistry and in situ spectroscopy has been contagious. He embodies what is meant by a “renaissance scientist”, as opposed to someone who is trained in a narrow branch of chemistry and does the same thing over and over. His latest drive to define sustainability, independent from social, political, and economic issues, could help to set achievable “BHAGs”67 for sustainable development. One last theme deserves emphasis. Horváth has always had the generous nature and open type of personality that makes it very easy for him to serve as a mentor, form personal relationships, and take special interest in the welfare of those around him. This also carries over to his family, which consists of a charming and professional wife (Rita) and an artistically gifted daughter (Julia). I have been enriched on personal and 9527



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phenyl-acetylene and/or Carbon Monoxide. Organometallics 1986, 5, 180. (10) Horváth, I. T. Preferential Retainment of the Cobalt-Rhodium Bond in Some Reactions of Co2Rh2(CO)12 and Its Triethylphosphine Substituted Derivatives. Organometallics 1986, 5, 2333. (11) Horváth, I. T.; Siskin, M. Direct Evidence for Formate Ion Formation during the Reaction of Coals with Carbon Monoxide and Water. Energy Fuels 1991, 5, 932. (12) Horváth, I. T.; Kastrup, R. V.; Oswald, A. A.; Mozeleski, E. J. High-Pressure NMR Studies on the Water Soluble Rhodium Hydroformylation System. Catal. Lett. 1989, 2, 85. (13) Brookhart, M.; Volpe, A. F.; Lincoln, D. M.; Horváth, I. T.; Millar, J. M. Detection of an Alkyl Ethylene Complex during Ethylene Polymerization by a Co(III) Catalyst. Energetics of the β-Migratory Insertion Reaction. J. Am. Chem. Soc. 1990, 112, 5634. (14) Baralt, E.; Smith, S. J.; Hurwitz, J.; Horváth, I. T.; Fish, R. H. Homogeneous Catalytic Hydrogenation. 6. Synthetic and Mechanistic Aspects of the Regioselective Reduction of Model Coal Nitrogen, Sulfur, and Oxygen Heteroaromatic Compounds Using the (η5Pentamethylcyclopentadienyl)rhodium Tris(acetonitrile) Dication Complex as the Catalyst Precursor. J. Am. Chem. Soc. 1992, 114, 5187. (15) Ferrughelli, D.; Horváth, I. T. Hydrodechlorination of Chloroaromatics. Bifunctional Homogeneous Rhodium Catalyst for the Conversion of Chloroaromatics to Saturated Hydrocarbons. J. Chem. Soc., Chem. Commun. 1992, 0, 806. (16) Moore, K.; Horváth, I. T.; Therien, M. J. High Pressure NMR Spectroscopic Studies of (Porphinato)Iron Catalyzed Isobutane Oxidation: Identification of Porphyrinic Species Present Under Catalytic Conditions when Dioxygen is Utilized as the Stoichiometric Oxidant. J. Am. Chem. Soc. 1997, 119, 1791. (17) Nozaki, K.; Hiyama, T.; Kacker, S.; Horváth, I. T. HighPressure NMR Studies on the Alternating Copolymerization of Propene with Carbon Monoxide Catalyzed by a Palladium(II) Complex of an Unsymmetrical Phosphine-Phosphite Ligand. Organometallics 2000, 19, 2031. (18) Charig, A.; Kinscherf, K.; Gariullo, B.; Roman, S.; Connors, T. F.; Unkefer, C.; Horváth, I. T. Synthesis and Characterization of [1,C14] N-methylneodecanamid. J. Labelled Compd. Radiopharm. 2000, 43, 177. (19) Csihony, S.; Mehdi, H.; Horváth, I. T. In Situ Infrared Spectroscopic Studies of the Friedel-Crafts Acetylation of Benzene in Ionic Liquids Using AlCl3 and FeCl3. Green Chem. 2001, 3, 307. (20) Tuba, R.; Mika, L. T.; Bodor, A.; Pusztai, Z.; Tóth, I.; Horváth, I. T. The Mechanism of the Pyridine Modified Cobalt-Catalyzed Hydromethoxycarbonylation of 1,3-Butadiene. Organometallics 2003, 22, 1582. (21) Mika, L. T.; Tuba, R.; Toth, I.; Pitter, S.; Horváth, I. T. Molecular Mapping of the Catalytic Cycle of the Cobalt-Catalyzed Hydromethoxycarbonylation of 1,3-Butadiene in the Presence of Pyridine in Methanol. Organometallics 2011, 30, 4751. (22) Pusztai, Z.; Vlád, G.; Bodor, A.; Horváth, I. T.; Laas, H. J.; Halpaap, R.; Richter, F. U. In situ NMR Observation of a Catalytic Intermediate in Phosphine Catalyzed Cyclooligomerization of Isocyanates. Angew. Chem., Int. Ed. 2006, 45, 107. (23) Csihony, S.; Mika, L. T.; Vlád, G.; Barta, K.; Mehnert, C. P.; Horváth, I. T. Oxidative Carbonylation of Methanol to Dimethyl Carbonate by Chlorine-Free Homogeneous and Immobilized 2,2’Bipyrimidine Modified Copper Catalyst. Collect. Czech. Chem. Commun. 2007, 72, 1094. (24) Fábos, V.; Lantos, D.; Bodor, A.; Bálint, A.-M.; Mika, L. T.; Sielcken, O. E.; Cuiper, A.; Horváth, I. T. ε-Caprolactamium Hydrosulfate: An Ionic Liquid Used in the Large Scale Production of ε-Caprolactam for Decades. ChemSusChem 2008, 1, 189. (25) Akien, G.; Qi, L.; Horváth, I. T. Molecular Mapping of the Acid Catalysed Dehydration of Fructose. Chem. Commun. 2012, 48, 5850. (26) Qi, L.; Horváth, I. T. Catalytic Conversion of Fructose to γValerolactone in γ-Valerolactone. ACS Catal. 2012, 2, 2247. (27) Millar, J. M.; Kastrup, R. V.; Melchior, M. T.; Horváth, I. T.; Hoff, C. D.; Crabtree, R. H. Kinetics by High-Pressure Nuclear

professional levels by our long-standing association, which is marked by a number of symmetries. We were born within one year of each other (1952/1953), married accomplished European women within one year of each other (1997), relocated from North America to Europe within one year of each other (1998/1999), and changed continents once more within one year of each other (2008/2009). Throughout all of these peregrinations, there has always been time to interact and relax, as illustrated in Figure 8 during a joint family outing. To István, everything described above is only the beginning. We all congratulate you on the occasion of your 65th birthday and your professional and personal achievement and look forward to many great things and cutting edge scientific contributions to come.

John Gladysz*

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Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

John Gladysz: 0000-0002-7012-4872 Notes

Views expressed in this editorial are those of the author and not necessarily the views of the ACS. The author declares no competing financial interest other than royalties from certain joint publications with the Festschrift honoree.

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ACKNOWLEDGMENTS The author thanks the Welch Foundation (Grant A-1656) for support.

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REFERENCES

(1) Sauer, J. C.; Cramer, R. D.; Engelhardt, V. A.; Ford, T. A.; Holmquist, H. E.; Howk, B. W. Bifurandione. I. Preparation and Characterization. J. Am. Chem. Soc. 1959, 81, 3677. (2) Váradi, G.; Horváth, I. T.; Palágyi, J.; Bak, T.; Pályi, G. The Influence of Tertiary Phosphorus Compounds on the Catalytic Synthesis of Bifurandions. J. Mol. Catal. 1980, 9, 457. (3) Horváth, I. T.; Pályi, G.; Markó, L.; Andreetti, G. Cobalt Carbonyls with Two Different Bridging Carbene Ligands: (μ2-But-2en-4-olid-4-ylidene)-μ2-(2’,2’-disubstituted-ethene-1’-ylidene)-dicobalt Hexacarbonyl Compounds. J. Chem. Soc., Chem. Commun. 1979, 1054. (4) Frank, J.; Dekany, G.; Pelczer, I.; Apsimon, J. W. The Composition of Primycin. Tetrahedron Lett. 1987, 28, 2759. (5) Adams, R. D.; Horváth, I. T.; Yang, L. W. The Use of Sulfido Ligands in the Synthesis of High Nuclearity Transition Metal Cluster Compounds. The Synthesis, Crystal and Molecular Structures of Os6(CO)17(μ4-S)2 and Os6(CO)16(μ4-S)(μ3-S). J. Am. Chem. Soc. 1983, 105, 1533. (6) Adams, R. D.; Horváth, I. T. Novel Reactions of Metal Carbonyl Cluster Compounds Prog. Inorg. Chem. 2007, 33, 127. (7) Adams, R. D.; Horváth, I. T.; Bonnet, J. J.; Bergounhou, C.; Attard, J. P. Thioosmium Clusters. Inorg. Synth. 1989, 26, 303. (8) Horváth, I. T.; Bor, G.; Garland, M.; Pino, P. Cobalt-Rhodium Heptacarbonyl: A Coordinatively Unsaturated Dinuclear Metal Carbonyl. Organometallics 1986, 5, 1441. (9) Horváth, I. T.; Zsolnai, L.; Huttner, G. Regiospecific Reactions of Cobalt-Rhodium Mixed-Metal Clusters. Unprecedented, Facile and Reversible Tetranuclear-Dinuclear Transformations Involving Di9528



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Magnetic Resonance: Reversible Hydrogen Binding in (η2-H2)Cr(CO)3[P(C6H11)3]2. J. Am. Chem. Soc. 1990, 112, 9643. (28) Horváth, I. T.; Cook, R. A.; Millar, J. M.; Kiss, G. LowTemperature Methane Chlorination with Aqueous Platinum Chlorides in the Presence of Chlorine. Organometallics 1993, 12, 8. (29) Selg, P.; Brintzinger, H. H.; Andersen, R. A.; Horváth, I. T. Coordination of CO to the Alkaline Earth Metallocene [(Me5C5)2Ca]. Angew. Chem., Int. Ed. Engl. 1995, 34, 791. (30) de Rege, P. J. F.; Gladysz, J. A.; Horváth, I. T. Spectroscopic Observation of the Formyl Cation in a Condensed Phase. Science 1997, 276, 776. (31) de Rege, P. J. F.; Gladysz, J. A.; Horváth, I. T. Facile and Selective Carbonylation of Methane in Superacids. Adv. Synth. Catal. 2002, 344, 1059. (32) Horváth, I. T.; Joó, F., Eds.; Aqueous Organometallic Chemistry and Catalysis; Kluwer Academic Publishers: Dordrecht, 1995. (33) Horváth, I. T. Water as Solvent for Catalysis. J. Mol. Catal. A: Chem. 1997, 116, 1. (34) Mika, L. T.; Cséfalvay, E.; Horváth, I. T. The role of water in catalytic biomass-based technologies to produce chemicals and fuels. Catal. Today 2015, 247, 33. (35) Horváth, I. T. Hydroformylation of Olefins with HRh(CO)[P(m-C6H4SO3Na)3]3 in SAP. Is It Really Aqueous? Catal. Lett. 1990, 6, 43. (36) Horváth, I. T. A Homogeneous Platinum Catalyst in the Stationary BF3.H2O Phase for the Hydrogenation of Arenes. Angew. Chem., Int. Ed. Engl. 1991, 30, 1009. (37) Horváth, I. T.; Rábai, J. Fluorous Multiphase Systems. U.S. Patent 5,463,082, 1995. (38) Horváth, I. T.; Rábai, J. Facile Catalyst Separation without Water: Fluorous Biphase Hydroformylation of Olefins. Science 1994, 266, 72. (39) Horváth, I. T. Fluorous Biphase Chemistry. Acc. Chem. Res. 1998, 31, 641. (40) Barabás, B.; Fülöp, O.; Molontay, R.; Pályi, G. Impact of the Discovery of Fluorous Biphasic Systems on Chemistry: A Statistical and Network Analysis. ACS Sustainable Chem. Eng. 2017, 5, 8108. (41) Juliette, J. J. J.; Horváth, I. T.; Gladysz, J. A. Transition Metal Catalysis in Fluorous Media: Practical Application of a New Immobilization Principle to Rhodium-Catalyzed Hydroboration. Angew. Chem., Int. Ed. Engl. 1997, 36, 1610. (42) Rutherford, D.; Juliette, J. J. J.; Rocaboy, C.; Horváth, I. T.; Gladysz, J. A. Transition Metal Catalysis in Fluorous Media: Application of a New Immobilization Principle to Rhodium Catalyzed Hydrogenation of Alkenes. Catal. Today 1998, 42, 381. (43) Juliette, J. J. J.; Rutherford, D.; Horváth, I. T.; Gladysz, J. A. Transition Metal Catalysis in Fluorous Media: Practical Application of a New Immobilization Principle to Rhodium-Catalyzed Hydroborations of Alkenes and Alkynes. J. Am. Chem. Soc. 1999, 121, 2696. (44) Guillevic, M.-A.; Arif, A. M.; Horváth, I. T.; Gladysz, J. A. Synthesis, Structure, and Oxidative Additions of a Fluorous Analog of Vaska’s Complex, trans-Ir(CO)(Cl)[P(CH2CH2(CF2)5CF3)3]2; Altered Reactivity in Fluorocarbons, and Implications for Catalysis. Angew. Chem., Int. Ed. Engl. 1997, 36, na. (45) Guillevic, M.-A.; Rocaboy, C.; Arif, A. M.; Horváth, I. T.; Gladysz, J. A. Organometallic Reactivity Patterns in Fluorocarbons, and Implications for Catalysis; Synthesis, Structure, Solubility, and Oxidative Additions of a Fluorous Analog of Vaska’s Complex, transIr(CO)(Cl)[P(CH2CH2(CF2)5CF3)3]2. Organometallics 1998, 17, 707. (46) Gladysz, J. A.; Curran, D. P., Horváth, I. T., Eds.; Handbook of Fluorous Chemistry; Wiley-VCH: Weinheim, 2004. (47) Horváth, I. T., Ed.; Fluorous Chemistry; Topics in Current Chemistry; Springer: Heidelberg, 2012. (48) Zhao, X.; Ng, W. Y.; Lau, K.-C.; Horváth, I. T.; Collis, A. E. C. Generation of perfluoro-t-butoxy-methyl ponytails for enhanced fluorous partition for aromatics and heterocycles. Phys. Chem. Chem. Phys. 2012, 14, 3909.

(49) Lo, S.-W.; Law, L.; Lui, M. Y.; Lau, K.-C.; Ma, C. Y.; Murphy, M. B.; Horváth, I. T.; Wei, X. G. Development of Sustainable Fluorous Chemistry: The Synthesis and Characterization of Fluorous Ethers and Diethers with Nonafluoro-tert-butoxy Groups. Org. Chem. Front. 2014, 1, 1180. (50) Horváth, I. T.; Mehdi, H.; Fábos, V.; Boda, L.; Mika, L. T. Gamma-valerolactone: A Sustainable Liquid for Energy and Carbonbased Chemicals. Green Chem. 2008, 10, 238. (51) Fábos, V.; Koczó, G.; Mehdi, H.; Boda, L.; Horváth, I. T. Biooxygenates and the Peroxide Number: A Safety Issue. Energy Environ. Sci. 2009, 2, 767. (52) Mehdi, H.; Fábos, V.; Tuba, R.; Bodor, A.; Mika, L. T.; Horváth, I. T. Integration of Homogeneous and Heterogeneous Catalytic Processes for a Multi-step Conversion of Biomass: from Sucrose to Levulinic acid, Gamma-valerolactone, 1,4-Pentanediol, 2Methyl-tetrahydrofuran, and Alkanes. Top. Catal. 2008, 48, 49. (53) Qi, L.; Mui, Y. F.; Lo, S. W.; Lui, M. Y.; Akien, G.; Horváth, I. T. Catalytic Conversion of Fructose, Glucose, and Sucrose to 5(hydroxymethyl)furfural and/or Levulinic and Formic Acids in γValerolactone as a Green Solvent. ACS Catal. 2014, 4, 1470. (54) Fábos, V.; Mika, L. T.; Horváth, I. T. Selective Conversion of Levulinic and Formic Acids to Gamma-Valerolactone with the ShvoCatalyst. Organometallics 2014, 33, 181. (55) Horváth, I. T. Green or Sustainable Chemistry or Both? Chem. Oggi − Chem. Today 2014, 32, 76. (56) Fábos, V.; Lui, M. Y.; Mui, Y. F.; Wong, Y. Y.; Mika, L. T.; Qi, L.; Cséfalvay, E.; Kovács, V.; Szű cs, T.; Horváth, I. T. The Use of Gamma-valerolactone as an Illuminating Liquid and Lighter Fluid. ACS Sustainable Chem. Eng. 2015, 3, 1899. (57) Tuck, C. O.; Perez, E.; Horváth, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of biomass: deriving more value from waste. Science 2012, 337, 695. (58) Cséfalvay, E.; Akien, G.; Qi, L.; Horváth, I. T. Definition and Application of Ethanol Equivalent: Sustainability Performance Metrics for Biomass Conversion to Carbon-based Fuels and Chemicals. Catal. Today 2015, 239, 50. (59) Cséfalvay, E.; Horváth, I. T. Sustainability Assessment of Renewable Energy in the United State, Canada, the European Unition, China, and the Russian Federation. ACS Sustainable Chem. Eng. 2018, 6, 8868. (60) Horváth, I. T.; Cséfalvay, E.; Mika, L. T.; Debreczeni, M. Sustainability metrics for biomass-based carbon chemicals. ACS Sustainable Chem. Eng. 2017, 5, 2734. (61) Horváth, I. T., Ed.; Encyclopedia of Catalysis, Vol. 1−6, Wiley: Hoboken, NJ, 2002. (62) Cornils, B.; Herrmann, W. A.; Horváth, I. T.; Leitner, W.; Mecking, S.; Olivier-Bourbigou, H.; Vogt, D., Eds.; Multiphase Homogeneous Catalysis; Wiley-VCH: Weinheim, 2005. (63) Horváth, I. T.; Malacria, M., Eds.; Advanced Green Chemistry, Part 1: Greener Organic Reactions and Processes; World Scientific: Singapore, 2018. (64) Horváth, I. T. Chemists should be aware of the environmental implication of their chemistry. Chem. Rev. 1995, 95, 1. (65) Horváth, I. T. Introduction: Sustainable Chemistry. Chem. Rev. 2018, 118, 369. (66) Náray-Szabó, G.; Mika, L. T. Conservative Evolution and Industrial Metabolism in Green Chemistry. Green Chem. 2018, 20, 2171. (67) Collins, J.; Porras, J. I. BHAGs: Big Hairy Audacious Goals. In Built To Last: Successful Habits of Visionary Companies. HarperBusiness: New York, 1994.

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Festschrift in Honor of IstvÃ¡n T. HorvÃ¡th - ACS Publications - American

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