Sustainable Catalysis With Non-endangered Metals Part 1 RSC Green Chemistry Editor-in-Chief: Professor James Clark, Department of Chemistry, University of York, UK Series Editors: Professor George A. Kraus, Department of Chemistry, Iowa State University, Ames, Iowa, USA Professor Andrzej Stankiewicz, Delft University of Technology, The Netherlands Professor Peter Siedl, Federal University of Rio de Janeiro, Brazil Titles in the Series: 1: The Future of Glycerol: New Uses of a Versatile Raw Material 2: Alternative Solvents for Green Chemistry 3: Eco-Friendly Synthesis of Fine Chemicals 4: Sustainable Solutions for Modern Economies 5: Chemical Reactions and Processes under Flow Conditions 6: Radical Reactions in Aqueous Media 7: Aqueous Microwave Chemistry 8: The Future of Glycerol: 2nd Edition 9: Transportation Biofuels: Novel Pathways for the Production of Ethanol, Biogas and Biodiesel 10: Alternatives to Conventional Food Processing 11: Green Trends in Insect Control 12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradation and Applications 13: Challenges in Green Analytical Chemistry 14: Advanced Oil Crop Biorefineries 15: Enantioselective Homogeneous Supported Catalysis 16: Natural Polymers Volume 1: Composites 17: Natural Polymers Volume 2: Nanocomposites 18: Integrated Forest Biorefineries 19: Sustainable Preparation of Metal Nanoparticles: Methods and Applications 20: Alternative Solvents for Green Chemistry: 2nd Edition 21: Natural Product Extraction: Principles and Applications 22: Element Recovery and Sustainability 23: Green Materials for Sustainable Water Remediation and Treatment 24: The Economic Utilisation of Food Co-Products 25:BiomassforSustainableApplications:PollutionRemediationandEnergy 26: From C–H to C–C Bonds: Cross-Dehydrogenative-Coupling 27: Renewable Resources for Biorefineries 28: Transition Metal Catalysis in Aerobic Alcohol Oxidation 29: Green Materials from Plant Oils 30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites and Nanocomposites 31: Ball Milling Towards Green Synthesis: Applications, Projects, Challenges 32: Porous Carbon Materials from Sustainable Precursors 33: Heterogeneous Catalysis for Today’s Challenges: Synthesis, Characterization and Applications 34: Chemical Biotechnology and Bioengineering 35: Microwave-Assisted Polymerization 36: Ionic Liquids in the Biorefinery Concept: Challenges and Perspectives 37: Starch-based Blends, Composites and Nanocomposites 38: Sustainable Catalysis: With Non-endangered Metals, Part 1 39: Sustainable Catalysis: With Non-endangered Metals, Part 2 40: Sustainable Catalysis: Without Metals or Other Endangered Elements, Part 1 41: Sustainable Catalysis: Without Metals or Other Endangered Elements, Part 2 How to obtain future titles on publication: Astandingorderplanisavailableforthisseries.Astandingorderwillbring delivery of each new volume immediately on publication. For further information please contact: BookSalesDepartment,RoyalSocietyofChemistry,ThomasGrahamHouse, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: þ44 (0)1223 420066, Fax: þ44 (0)1223 420247 Email: [email protected] Visit our website at www.rsc.org/books Sustainable Catalysis With Non-endangered Metals Part 1 Edited by Michael North Green Chemistry Centre of Excellence, University of York, York, UK Email: [email protected] RSCGreenChemistryNo.38 PrintISBN:978-1-78262-638-1 PDFeISBN:978-1-78262-211-6 ISSN:1757-7039 AcataloguerecordforthisbookisavailablefromtheBritishLibrary rTheRoyalSocietyofChemistry2016 Allrightsreserved Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor privatestudy,criticismorreview,aspermittedundertheCopyright,DesignsandPatents Act1988andtheCopyrightandRelatedRightsRegulations2003,thispublicationmaynot bereproduced,storedortransmitted,inanyformorbyanymeans,withouttheprior permissioninwritingofTheRoyalSocietyofChemistryorthecopyrightowner,orinthe caseofreproductioninaccordancewiththetermsoflicencesissuedbytheCopyright LicensingAgencyintheUK,orinaccordancewiththetermsofthelicencesissuedby theappropriateReproductionRightsOrganizationoutsidetheUK.Enquiriesconcerning reproductionoutsidethetermsstatedhereshouldbesenttoTheRoyalSocietyof Chemistryattheaddressprintedonthispage. TheRSCisnotresponsibleforindividualopinionsexpressedinthiswork. Theauthorshavesoughttolocateownersofallreproducedmaterialnotintheirown possessionandtrustthatnocopyrightshavebeeninadvertentlyinfringed. PublishedbyTheRoyalSocietyofChemistry, ThomasGrahamHouse,SciencePark,MiltonRoad, CambridgeCB40WF,UK RegisteredCharityNumber207890 Forfurtherinformationseeourwebsiteatwww.rsc.org Preface The12principlesofgreenchemistrywereoriginallyreportedbyAnastas1 intheformshowninBox1andlaterasthemnemonicshowninBox2by Poliakoff.2 A feature of these principles is the use of catalytic reagents to accomplish chemical transformations. The development of catalysts for important chemical transformations certainly predates any notion of green chemistry and has been a major feature of research in all areas of chemistry for almost 150 years. Thus, physical chemists and material scientists have dominated the development of heterogeneous catalysis; physical and physical organic chemists have developed tools to allow catalytic cycles to be determined. Inorganic and organic chemists have developed new ligands and catalysts for homogeneous metal-based catalysts and organic chemists have shown that metal-free asymmetric catalysis can be achieved. Finally, biological chemists have studied the mechanisms of enzyme-catalysed reactions and developed new biochemical tools that allow the structure of enzymes to be modified to enhance their catalytic activity for a particular substrate, or even allow them to catalyse a different reaction. There have been some remarkable achievements in catalyst development recognisedbynumerousNobelprizesforworkdoneinthisarea(Box3)and catalysis has progressed to the stage where it is now difficult to imagine a reaction that cannot be achieved catalytically. However, examination of the catalyticliteratureshowsthatthemajorityofcatalystsdeveloped,andmany that are in commercial use rely upon the use of metals or other elements whose abundance in the Earth’s crust is very limited and that are being rapidly consumed. This is illustrated in Figure 1 for papers on asymmetric catalysis published between 1999 and 2005.3 RSCGreenChemistryNo.38 SustainableCatalysis:WithNon-endangeredMetals,Part1 EditedbyMichaelNorth rTheRoyalSocietyofChemistry2016 PublishedbytheRoyalSocietyofChemistry,www.rsc.org vii viii Preface Box 1 The 12 principles of green chemistry according to Anastas 1. Itisbettertopreventwastethantotreatorcleanupwasteafteritis formed. 2. Synthetic methods should be designed to maximise the in- corporation of all materials used in the process into the final product. 3. Whereverpracticable,syntheticmethodologiesshouldbedesigned to use and generate substances that possess little or no toxicity to human health and the environment. 4. Chemical products should be designed to preserve efficacy of function while reducing toxicity. 5. The use of auxiliary substances (e.g. solvents, separation agents etc.) should be made unnecessary wherever possible and innocu- ous when used. 6. Energy requirements should be recognized for their environ- mentalandeconomicimpactandshouldbeminimized.Synthetic methods should be conducted at ambient temperature and pressure. 7. A raw material or feedstock should be renewable rather than de- pleting wherever technically and economically practicable. 8. Unnecessary derivatization (blocking group, protection/deprotec- tion, temporary modification of physical/chemical processes) should be avoided whenever possible. 9. Catalytic reagents (as selective as possible) are superior to stoi- chiometric reagents. 10. Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products. 11. Analyticalmethodologiesneedtobefurtherdevelopedtoallowfor real-time,in-processmonitoringandcontrolpriortotheformation of hazardous substances. 12. Substancesandtheformofasubstanceusedinachemicalprocess should be chosen so as to minimise the potential for chemical accidents, including releases, explosions and fires. The availability of chemical elements depends on many factors as discussed in Chapter 1 of Sustainable Catalysis: With Non-endangered Metals,Part1.Withtheexceptionofhelium,whichistoolighttobeheldby the Earth’s gravity and so is lost to space, chemical elements are not actually being lost to planet Earth, rather they are being transferred from relatively rich ores to much more diluted waste sites from where, in most Preface ix Box 2 The green chemistry mnemonic developed by Poliakoff P – Prevent wastes R – Renewable materials O – Omit derivatization steps D – Degradable chemical products U – Use safe synthetic methods C – Catalytic reagents T – Temperature, pressure ambient I – In process monitoring V – Very few auxiliary substances E – E-factor, maximise feed in product L – Low toxicity of chemical products Y – Yes, it is safe cases, it is not currently economically viable to recover them. This, combined with growing demand for many elements, often low recycling ratesandgeographicalandpoliticalrestrictionsonoreavailabilityleadsto the concept of elemental sustainability. One pictorial representation of elemental sustainability is shown in Figure 24 and this, along the British GeologicalSurvey2012Risklist(BGS2012)5whichrankedthesupplyriskof elements from10(high)to 1(low) forms thebasisof therestofthis book. Thus, catalysts that contain only elements coloured green or orange in Figure 2 and that have a relative supply risk index of 7.6 or lower in the BGS2012areincludedinthisbookwiththreeexceptions.Palladiumwould have been borderline to include (orange in Figure 2 and supply risk index of7.6inBGS2012),buthasbeenexcludedasitissowidelyusedincatalysis that it would have required a separate volume to cover its use in catalysis. Achapteronscandiumandyttriumbasedcatalystswasplannedbutcould not be delivered due to the author’s ill health. After an introductory chapter on elemental sustainability, the first two volumes of this work, Sustainable Catalysis: With Non-endangered Metals, Parts 1 and 2, deal with sustainable metal based catalysts. Within each subsequentchapter,theauthorshavebeenaskedtoexcludeanycatalystthat contains ligands containing endangered elements (e.g. phosphorus) and to highlight any examples that have other sustainable features (use of green solvent, high atom economy, etc.). Where appropriate, elements have been grouped together (e.g. thealkali metals inChapter 2) and those metals that are most commonly used in catalysis have been given multiple chapters: Chapters 4–7 for titanium, 12–13 for iron and 18–19 for aluminium. The finalthreechaptersofPart2dealwiththallium,tinandleadbasedcatalysts. Theseareincludedforcompletenessastheymeettherequirementsoutlined x Preface Box 3 Nobel prizes for catalysis (up to 2014) 2010:RichardF.Heck,Ei-ichiNegishiandAkiraSuzukiforpalladium- catalysed cross couplings in organic synthesis. 2007: Gerhard Ertl for studies of chemical processes on solid surfaces 2005: Yves Chauvin, Robert H. Grubbs and Richard R. Schrock for the development of the metathesis method in organic syn- thesis. 2001: William S. Knowles, Ryoji Noyori and K. Barry Sharpless for work on chirally catalysed hydrogenation and oxidation reactions. 1997: Paul D. Boyer, John E. Walker and Jens C. Skou for the eluci- dation of the enzymatic mechanism underlying the synthesis of adenosine triphosphate (ATP) and the first discovery of an ion- transporting enzyme, Na1, K1 -ATPase. 1989: Sidney Altman and Thomas R. Cech for the discovery of the catalytic properties of RNA. 1975: John Warcup Cornforth and Vladimir Prelog for work on the stereochemistryofenzyme-catalyzed reactionsandresearch into the stereochemistry of organic molecules and reactions. 1972: Christian B. Anfinsen, Stanford Moore and William H. Stein for workonribonuclease,especiallyconcerningtheconnectionbetween the amino acid sequence and the biologically active conformation andforcontributiontotheunderstandingoftheconnectionbetween chemical structure and catalytic activity of the active centre of the ribonuclease molecule. 1963: Karl Ziegler and Giulio Natta for their discoveries in the field of the chemistry and technology of high polymers. 1929: Arthur Harden and Hans Karl August Simon von Euler-Chelpin for their investigations on the fermentation of sugar and fermen- tative enzymes. 1918: Fritz Haber for the synthesis of ammonia from its elements. 1912: Victor Grignard and Paul Sabatier for the discovery of the so- called Grignard reagent, which in recent years has greatly advanced the progress of organic chemistry and for the method of hydrogen- ating organic compounds in the presence of finely disintegrated metals whereby the progress of organic chemistry has been greatly advanced in recent years. 1909: Wilhelm Ostwald in recognition of his work on catalysis and for his investigations into the fundamental principles governing chem- ical equilibria and rates of reaction.