ADVISORY BOARD L H Gade D Darensbourg Universität Heidelberg Germany Texas A & M University College Station, Texas, USA M L H Green H B Gray University of Oxford Oxford, United Kingdom California Institute of Technology Pasadena, California, USA A E Merbach P A Lay Laboratoire de Chimie et Bioanorganique EFPL, Lausanne, Switzerland University of Sydney Sydney, Australia P J Sadler J Reedijk University of Warwick Warwick, England Leiden University Leiden, The Netherlands K Wieghardt Y Sasaki Max-Planck-Institut Mülheim, Germany Hokkaido University Sapporo, Japan Academic Press is an imprint of Elsevier 225 Wyman Street, Waltham, MA 02451, USA 525 B Street, Suite 1800, San Diego, CA 92101-4495, USA 32 Jamestown Road, London NW1 7BY, UK The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, UK Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands First edition 2014 Copyright © 2014, Elsevier Inc All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@elsevier.com Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-12-420221-4 ISSN: 0898-8838 For information on all Academic Press publications visit our website at store.elsevier.com Printed and bound in USA 14 15 16 17 11 10 CONTRIBUTORS Antonella Angelini Department of Chemistry, University of Bari, Bari, Italy Michele Aresta CIRCC Via Celso Ulpiani 27, Bari, Italy Arno Behr Technical Chemistry, Department of Bio- and Chemical Engineering, Technical University of Dortmund, Dortmund, Germany Robert H Carr Huntsman (Europe)bvba, Kortenberg, Belgium Donald J Darensbourg Department of Chemistry, Texas A&M University, College Station, Texas, USA Zhen-Feng Diao State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, P R China Angela Dibenedetto CIRCC Via Celso Ulpiani 27, and Department of Chemistry, University of Bari, Bari, Italy Etsuko Fujita Chemistry Department, Brookhaven National Laboratory, Upton, New York, USA Kyle A Grice Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, USA Liang-Nian He State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, P R China Richard H Heyn SINTEF Materials and Chemistry, Blindern, Oslo, Norway Yuichiro Himeda National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, and Japan Science and Technology Agency, Kawaguchi, Saitama, Japan Ivo Jacobs Huntsman Holland BV, Rotterdam, The Netherlands Konstantin Kraushaar Institut fuăr Anorganische Chemie, Arbeitsgruppe Siliciumchemie und Chemische Materialwissenschaft, Technische Universitaăt Bergakademie Freiberg, Freiberg, Germany ix x Contributors Edwin Kroke Institut fuăr Anorganische Chemie, Arbeitsgruppe Siliciumchemie und Chemische Materialwissenschaft, Technische Universitaăt Bergakademie Freiberg, Freiberg, Germany Clifford P Kubiak Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, USA Yu-Nong Li State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, P R China Hannu-Petteri Mattila Thermal and Flow Engineering Laboratory, A˚bo Akademi University, Turku, Finland James T Muckerman Chemistry Department, Brookhaven National Laboratory, Upton, New York, USA Kristina Nowakowski Technical Chemistry, Department of Bio- and Chemical Engineering, Technical University of Dortmund, Dortmund, Germany Dana Schmidt Institut fuăr Anorganische Chemie, Arbeitsgruppe Siliciumchemie und Chemische Materialwissenschaft, Technische Universitaăt Bergakademie Freiberg, Freiberg, Germany Anke Schwarzer Institut fuăr Anorganische Chemie, Arbeitsgruppe Siliciumchemie und Chemische Materialwissenschaft, Technische Universitaăt Bergakademie Freiberg, Freiberg, Germany Wan-Hui Wang National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, and Japan Science and Technology Agency, Kawaguchi, Saitama, Japan Zhen-Zhen Yang State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, P R China Ron Zevenhoven Thermal and Flow Engineering Laboratory, A˚bo Akademi University, Turku, Finland PREFACE Volume 66 of Advances in Inorganic Chemistry is a thematic volume devoted to CO2 chemistry, co-edited by Michele Aresta from the University of Bari, Italy At the recent 4th EuCheMS Chemistry Congress in Prague, August 2012, a special symposium on CO2 chemistry was organized as part of the Inorganic Chemistry Program Understanding the important industrial and environmental role of CO2 effluents is a multidisciplinary challenge to scientists working on various aspects of CO2 chemistry with the ambitious target of converting large volumes of CO2 for an effective carbon recycling Should the latter be implemented, it would result in a significant environmental benefit with fossil reserves preservation for future generations A number of speakers at this symposium and other leading scientists working in this area were invited to contribute to this special issue The contributed chapters cover an important part of CO2 utilization strategies In the opening chapter, Donald J Darensbourg presents a personal account on his adventures in the synthesis of copolymers from CO2 and cyclic ethers This is followed by a chapter on the synthesis of organic carbonates by Angela Dibenedetto and Antonella Angelini In Chapter 3, Richard H Heyn, Ivo Jacobs, and Robert H Carr report on the synthesis of aromatic carbamates from CO2 and the implications for the polyurethane industry This is followed by a chapter on the reactions of CO2 and CO2 analogs with reagents containing Si–H and Si–N units reported by Konstantin Kraushaar, Dana Schmidt, Anke Schwarzer, and Edwin Kroke In Chapter 5, Kyle A Grice and Clifford P Kubiak report on recent studies of rhenium and manganese bipyridine carbonyl catalysts for the electrochemical reduction of CO2 In the subsequent chapter, Wan-Hui Wang, Yuichiro Himeda, James T Muckerman, and Etsuko Fujita discuss the interconversion of CO2/H2 and formic acid under mild conditions in water and focus on ligand design for effective catalysis Chapter is devoted to the catalytic hydrogenation of CO2 to formic acid by Arno Behr and Kristina Nowakowski This is followed by a report on the conversion of “exhaust” carbon into “working” carbon by Michele Aresta, Angela Dibenedetto, and Antonella Angelini In Chapter 9, Yu-Nong Li, Liang-Nian He, ZhenFeng Diao, and Zhen-Zhen Yang present a report on carbon capture with simultaneous activation and subsequent transformation In the final contribution, Hannu-Petteri Mattila and Ron Zevenhoven present an account on xi xii Preface the production of precipitated calcium carbonate from steel converter slag and other calcium-containing industrial wastes and residues We are most appreciative of the efforts of the authors and their colleagues who have provided informative, instructive, and authoritative contributions for this thematic volume We believe researchers in the field of CO2 chemistry will be encouraged by presented contributions in this volume We invite readers in other fields of chemistry to acquaint themselves with the fascinating and intriguing chemical challenges awaiting us MICHELE ARESTA CIRCC, University of Bari, Bari, Italy RUDI VAN ELDIK University of Erlangen-Nuărnberg, Erlangen, Germany October 2013 CHAPTER ONE Personal Adventures in the Synthesis of Copolymers from Carbon Dioxide and Cyclic Ethers Donald J Darensbourg Department of Chemistry, Texas A&M University, College Station, Texas, USA Contents Introduction Carbon Dioxide as a Source of Chemical Carbon Copolymers from Oxiranes and Carbon Dioxide Block Copolymers of Polycarbonates and Lactides Terpolymers from Oxiranes and Carbon Dioxide Depolymerization of Polycarbonates Acknowledgments References 12 13 19 22 22 Abstract This chapter focuses on recent advances in the development of well-defined metal catalysts for the coupling of CO2 and oxiranes for the production of polycarbonates and cyclic carbonates Since this subject has been comprehensively covered in several reviews recently, this treatment will center on contributions from our laboratory within the context of other published work Special attention will be given to our current studies dealing with depolymerization pathways of polymeric materials derived from completely alternating copolymerization of CO2 and epoxides Keywords: Carbon dioxide, Copolymerization, Terpolymerization, Epoxides, Metal catalysts, Polycarbonates, Salen ligands INTRODUCTION The interest of my research program in the organometallic chemistry of carbon dioxide began in the mid-1970s when we were investigating the mechanistic aspects of group metal carbonyl-catalyzed water–gas shift reactions These studies eventually led us to examining in detail the insertion Advances in Inorganic Chemistry, Volume 66 ISSN 0898-8838 http://dx.doi.org/10.1016/B978-0-12-420221-4.00001-9 # 2014 Elsevier Inc All rights reserved Donald J Darensbourg reactions of CO2 into MdOH and MdOR (R ¼ alkyl or aryl) bonds We and others definitively established that insertion of CO2 into metaldOR bonds occurred in the absence of prior coordination of CO2 to the metal center (1, 2) That is, the major interaction in the transition state (TS) involves the electrophilic carbon center of CO2 with a lone pair on the nucleophilic oxygen atom of the OR group as depicted in Figure 1.1 Consistent with this interpretation, the rate of this reaction is highly dependent on the nucleophilicity of the metal alkoxide moiety since CO2 is such a poor electrophile As indicated in Figure 1.1, the reaction is reversible although the metal carbonate is generally thermodynamically more stable than the corresponding metal alkoxide and CO2 The reaction described in Figure 1.1 is one of the pivotal steps in the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates (see Equation 1.1) This is particularly relevant since the most prominent metal catalysts for this process, for example, (salen)CrCl (salen ¼ salicylaldimine), upon binding the growing polymer chain, are coordinatively saturated In this chapter, I will describe our most recent advances in the development of well-defined metal catalysts for the coupling reactions of CO2 and cyclic ethers (oxiranes) for the production of polycarbonates or cyclic carbonates These studies will focus on contributions from our laboratory within the context of other published work This subject matter has been comprehensively covered in numerous reviews, including one which chronologically described developments in this field starting with the pioneering efforts of Inoue and coworkers (3) Prior to summarizing our recent results on the utilization of CO2 to produce polymeric materials, it is useful to assess the issues surrounding the use of CO2 in organic synthesis O O O + CO2 metal catalyst O O polycarbonate + O O cyclic carbonate dO O C [M] OR + CO2 d+ [M] ð1:1Þ n O C [M] O O R Figure 1.1 Carbon dioxide insertion pathway into metaldOR bond OR Personal Adventures in the Synthesis of Copolymers from CO2 CARBON DIOXIDE AS A SOURCE OF CHEMICAL CARBON Presently in the United States, we are experiencing the discovery of additional petroleum deposits and the development of new technologies for its recovery, albeit often with a negative environmental impact Nevertheless, if we continue to consume this finite source of prereduced carbon in particular as fuels, concomitantly emitting the oxidized carbon to the atmosphere, we not only will lead to climate change but also will exhaust this source of chemical carbon This situation clearly does not satisfy the EPA’s definition of sustainability, that is, “meeting the needs of the present without compromising the ability of future generations to meet their own needs.” At this point, the only reservoirs of carbon for chemical synthesis will be immediate biomass and carbon dioxide Of course, coupled with this occurrence is the fact that the world population is projected to increase by 50% by 2044 to billion, along with an increase in the economies of this emerging population growth The current uses of CO2 for chemical synthesis are quite limited, with the major industrial processes being the synthesis of urea, salicylic acid, methanol, and inorganic carbonates (4) More recently, a sizable quantity of CO2 is utilized in a greener synthesis of BPA-derived polycarbonate, which avoids the use of the very toxic phosgene reagent (see Equation 1.2) That is, Asahi Kasei Corporation has solved the engineering problems associated with the disfavored equilibria involved in the synthesis of diphenyl carbonate from dimethyl carbonate via ethylene carbonate, the latter reagent being readily synthesized from ethylene oxide and CO2 (5) Of importance, the coproduct in this reaction, ethylene glycol, is a commodity chemical that is generally produced by hydration of ethylene oxide All other reagents are recycled in the process (see Figure 1.2): O n PhO PhO + n HO OH melt O O O C + 2n PhOH n ð1:2Þ The largest obstacle for establishing industrial processes based on the use of CO2 as a raw material is the high energy required to transform CO2 because of its low-energy level Hence, processes involving nonrenewable sources of energy require the use of high-energy starting materials Donald J Darensbourg O PhO OPh bis-phenol A PhOH BPA polycarbonate O CO2 + O O O O MeOH MeO OMe DMC + HOCH2CH2OH Ethylene glycol Figure 1.2 Asahi Kasei’s nonphosgene route to BPA polycarbonate, products in red and recyclables in green The reaction described in Equation (1.1) fits this requirement, being based on small-membered ring compounds and affording oxidized low-energy synthetic targets COPOLYMERS FROM OXIRANES AND CARBON DIOXIDE Our initial report utilizing binary (salen)CrCl catalyst systems for the copolymerization of cyclohexene oxide or propylene oxide and carbon dioxide provided the stimulus for the development of the most productive and selective catalysts currently studied (6, 7) That is, the use of these complexes and their cobalt(III) and aluminum(III) analogs, and their closely related porphyrin derivatives, has dominated studies leading to effective copolymerization processes of CO2 with a variety of epoxides (3) This chemistry has evolved to the point today that most active and selective catalyst systems are composed of bifunctional catalysts where the cocatalyst is covalently attached to the salen ligand (8–10) Scheme 1.1 summarizes the accepted mode of reaction of these catalyst systems, where the cocatalyst is an onium salt composed of various anion initiators It is noteworthy to recall from our earlier studies in organometallic chemistry that the CO2 insertion step does not require prior coordination of CO2 to the coordinatively saturated metal center Additionally, at modest CO2 pressures where insertion of CO2 is not rate-limiting, the slow step is proposed to involve ring-opening of a bound epoxide substrate by the carbonate end group of the growing polymer chain The more detailed pathways for production of the thermodynamically stable five-membered cyclic carbonate are illustrated in Scheme 1.2 In our early study, we clearly demonstrated that employing the (salen)CrCl catalyst system, the selectivity for 390 I Imidazolidinones, synthesis of, 64s Imidazolium IL-promoted cyclic carbonate synthesis, 323, 324s Indirect carbonation process, PCC production, 361–362 brown coal fly ash, 360 of cement and concrete sludge, 362 reactor setup for, 375–377, 376f schematic representation, 365–366, 365f Industrial waste materials, PCC production, 356, 357t ammonium chloride solutions, 361 brine solution and fly ash, carbonation of, 361 cement kiln dust, 360 elemental composition of, 349, 351t gypsum waste carbonation, 362 oil shale ash indirect aqueous carbonation, 356–359 paper bottom ash, 361 salty water carbonation, 359 Infrared spectroelectrochemistry (IR-SEC), 170–171 Innovative synthesis, organic carbonates carbon dioxide reactant carboxylation of ethanol, 41s direct carboxylation of alcohols, 36 DRIFT studies, 38 hemicarbonate species, 32–33, 32f n-dibutyldialkoxy stannanes, 32 phosgene-free synthesis, 30–41 quasi-neutral reaction, 31 urea utilization alcoholysis, 41s catalytic distillation process, 41–42 Inorganic alkali absorbents, CO2 capture, 294 In situ infrared spectroscopy, poly(styrene carbonate), 12–13 Ionic liquids (ILs), 295 See also Task-specific ionic liquid (TSIL) absorbents in CO2 and aniline, 101t effects of, 99 HPLC, 100 IL/Ni(OAc)2 ratio vs alcohol/aniline ratio, 108f N-methyl-and N,N-dimethylaniline, 104–107, 107f Index screening products, 105f, 106f working definition, 99 Iridium based catalysts, in CO2 hydrogenation, 230, 240–244 Iron and steelmaking slags chemical composition of, 349, 352t mineralogical compositions of, 363, 364t Iron–pincer complex, 246, 247f Isocyanates, 334, 335s with bis-silylated urea, 142 N,N’-silylated urea formation, 136 K Kinetic isotope effect (KIE), 173–174 in CO2 hydrogenation, 205–206, 206t L Leaching studies, on steel slags, 366 Lewis basic ILs, for cyclic carbonate synthesis, 324, 325s Life-cycle assessment (LCA), of organic carbonate synthesis, 268–269 Lime-soda process, PCC production, 354 Liquid absorbents, CO2 capture aqueous alkanolamine absorbents 2-amino-2-methyl-1-propanol, 294 diethanolamine, 293–294 drawbacks, 294–295 monoethanolamine, 293–294 N-methyldiethanolamine, 293–294 2-piperidineethanol, 294 inorganic alkali absorbents, 294 TSIL absorbents amino-functionalized TSIL, 295–298 superbase-derived TSIL, 298–304 M MDA phosgenation of, 88–89, 88f production of, 87–88, 88f Metal carbonyl-catalyzed water-gas shift reactions, 1–2 Metallo-organic framework (MOF), for epoxide carboxylation, 46 Methylene diphenylene diisocyanate (MDI), 87 3-Methyl-1-phenyl-1-(trimethylsilyl)urea, 139s 391 Index Mineral carbonation process, PCC production, 355–356 Miniplant scale, CO2 hydrogenation catalyst phase, recycling of, 252, 252f general flow sheet, 250, 250f initial pressures vs reaction operations, 251, 251f liquid–liquid multiphase systems, 247, 249–250, 249f preliminary batch experiments formic acid–triethylamine salt formation, 249, 249f ruthenium(III)tris(acetylacetonate), 247–248, 248f tertiary amines, 248, 248t Mitsunobu reagent, 315–316, 332–333, 334 fac-Mn(bpy-R)(CO)3X cyclic voltammograms, 181 electrochemical response, 181, 181f vs Re(bpy-R)(CO)3X, 182, 182t structural and spectroscopic comparison, 183t X-ray crystal structure, 180–181, 183f N NaZSM-5 zeolite-catalyzed transesterification, of cyclic carbonate, 327–328, 328s NMR spectroscopic analysis, 147 Nonprecious metal catalysts, in CO2 hydrogenation, 244–246, 245t N-silylated ureas, 125 O Oil shale ash indirect aqueous carbonation, PCC production, 356–359 Organic carbonates cyclic carbon dioxide and diol reaction, 56 carbon dioxide or urea with glycerol, 58–62 carboxylation of epoxides, 44–49 cyclic alkylene carbonate reactivity, 62–64 cyclic ketals with carbon dioxide reaction, 54 oxidative carboxylation of olefins, 49–52 from propargyl alcohol, 54–55 structure, 26, 26f synthesis from halohydrins, 52–54 urea and diol reaction, 57–58 linear conventional synthesis, 28–30 innovative synthesis, 30–44 structure, 26f market and production, 27 organic cyclic carbonates, 27 transesterification reactions cyclic carbonate synthesis, 68–70 linear carbonate synthesis, 64–68 Overall efficiency, fuel-forming system, 165–166 Oxazolidinone synthesis, 64s from amino alcohol and CO2 carboxylation of, 316 dehydration, 315, 315s Mitsunobu reaction, 315–316, 316s from aziridine and CO2 catalyst-free process, 314, 315s ionic liquid catalysts, 308–312 polystyrene-supported catalyst, 312–313 quaternary ammonium salt catalysts, 305–308 zirconyl chloride, 313–314 from olefin, nitrogen source and CO2, 317–318 from propargylic alcohol, aliphatic primary amine and CO2, 317 uses of, 304–305 Oxidative carbonylation reactions, 92f P Palladium catalysts, in CO2 hydrogenation, 240 Parr reactor, 111 PCC production See Precipitated calcium carbonate (PCC) production Peris’s N-heterocyclic carbene complex, for CO2 hydrogenation, 197, 197f Phosgenation MDA, 88–89, 88f organic carbonates, 95 toluene diamines, 86–87 Phosgene-free synthesis of organic carbonates, 30 392 Photochemical CO2 reduction constitutional device elements, 278, 279f issues, 278–280, 279f mode of action, 278 requirements, 282–283 Photoelectrochemical CO2 reduction, 283 Photovoltaics (PV) hydrogen production, 275–276 methanol production, 276 Poly(cyclohexene carbonate), 10–11 Polycarbonates, depolymerization of, 19–22 Polyisocyanate reactions, 85f Polyurethane (PUs), 85, 112 Precipitated calcium carbonate (PCC) production calcitech process, 354 carbonation process, 350–352, 353f carbon dioxide for, 349 consumption of, 348–349, 349f existing technologies for, 350, 353t filler recycling process, 355 financial benefit, 380 in global scale, 378–380 vs ground calcium carbonate, 348–349 industrial waste materials, 356, 357t ammonium chloride solutions, 361 brine solution and fly ash, carbonation of, 361 cement kiln dust, 360 elemental composition of, 349, 351t gypsum waste carbonation, 362 oil shale ash indirect aqueous carbonation, 356–359 paper bottom ash, 361 salty water carbonation, 359 lime-soda process, 354 mineral carbonation process, 355–356 Solvay process, 353–354 steel slag carbonation calcium carbonate precipitation, 371–375 calcium extraction, 366–369 direct vs indirect aqueous carbonation, 365–366 Finnish steel converter slag carbonation process, 375–378 Index leaching studies, 366 vanadium extraction, 370 waste streams from steelmaking process, 363–365 Q Quinazoline synthesis, 330–331 R Racemization, 139 Reductive carbonylation reactions, 92f Reversible hydrogen storage, formic acid vs H2/CO2 interconversion, 217–219 fac-Re(bpy-R)(CO)3X anion studies bonding interactions, 177–179, 179f EXAFS experiments, 179–180 FTIR spectra, 175–176 highest occupied molecular orbital (HOMO), 177–179, 178f molecular structure, 175–176, 176f UV–vis spectroscopy, 177–179, 178f X-ray absorption studies, 179–180 X-ray crystal structure, 176–177, 177t CO2 reduction catalysts Brønsted acids, 171–172 cyclic voltammogram, 168–169, 168f 1e– and 2e– pathway, 168–169 infrared spectroelectrochemistry, 170–171 kinetic isotope effect, 173–174 polymerization, 184–185 UV–Vis absorption spectra of, 169–170 electrochemical and spectroscopic studies acetonitrile, 172, 173f kinetic isotope effect, 173–174 semiconductor electrodes, 174–175 general structure, 166–167, 166f geometry, 167–168 photochemistry, 167–168 structural and spectroscopic comparison, 183t Rhodium catalysts, in CO2 hydrogenation, 236–239, 237t Ruthenium catalysts, in CO2 hydrogenation, 231–235, 232t 393 Index S Salty water carbonation, PCC production, 359 Silicon–nitrogen bonds, CO2 insertion reactions into bis(trimethylsilyl)-benzamidinato fragment, 127–128 carbamoyloxysilanes, 121t di(alkylamino)dimethylsilane decomposition, 127, 127s electron-rich silylated nitrogen heterocycles, 124 exothermic reaction, 121–122 hexamethyldisilazane and CO2, 123–124 isocyanates and isothiocyanates, 136–152 isoelectronic molecules, 132–135 Nb complex, 128 nonacyclic ring structures, 123s N-siloxycarbonylation of diazoles, 124–125 N-silylated ureas, 125 thermodynamic driving force, 120 Silylated poly urea derivatives, applications of, 154s Silylcarbamate applications herbicides, 153 as reagent in organic chemistry, 153 silylation reagent, 152 Slag2PCC process, 375, 376f Sodium cyanate production, 94f Solar energy conversion, efficiency of, 274–275, 275s Solvay process, PCC production, 353–354 S–silyl–N,N-dialkylmonocarbamates, 133–134 Steel converter slag calcium extraction ammonium chloride, 367 chemical compositions of, 366–367, 368t dissolved carbon dioxide vs pH, 367, 369f efficiency, 367 limitations for, 369, 370f tributyl phosphate, 367 direct vs indirect aqueous carbonation, 365–366 vanadium extraction, 370 Steelmaking process, waste streams, 363–365 Steel slag carbonation, PCC production calcium carbonate precipitation, 371–375 calcium extraction, 366–369 direct vs indirect aqueous carbonation, 365–366 Finnish steel converter slag carbonation process, 375–378 leaching studies, 366 vanadium extraction, 370 waste streams from steelmaking process, 363–365 Substituted ureas, 94–95 Superbase-derived TSIL DBU/PEG system, 302–303, 303s diamine-carbon dioxide reaction, 304, 305s and hydroxyl-functionalized ILs, 298–299, 300s imidazolium ILs with C-2 hydrogen, 301, 301s pKa values in DMSO, 302, 303s protic ionic liquids, 301–302, 302s Supercritical carbon dioxide (scCO2), hydrogenation of, 227 Sustainability, definition of, T Task-specific ionic liquid (TSIL) absorbents, 294–304 amino-functionalized TSIL amino acid-derived tetraalkylammonium ILs, 296–297, 297s a-amino acids, 296 [Choline][Pro] synthesis, 297–298, 298s CO2 chemisorption, 295, 295s dual amino-functionalized phosphonium ILs, 298, 299s N-substituted amino acid salts, 298, 299s superbase-derived TSIL DBU/PEG system, 302–303, 303s diamine-carbon dioxide reaction, 304, 305s 394 Task-specific ionic liquid (TSIL) absorbents (Continued ) and hydroxyl-functionalized ILs, 298–299, 300s imidazolium ILs with C-2 hydrogen, 301, 301s pKa values in DMSO, 302, 303s protic ionic liquids, 301–302, 302s Terpolymerization, from oxiranes and carbon dioxide Co(III) catalyst, 14s Fineman–Ross plot, 16, 16f GPC traces, 15f one-pot process, 18 pKb of cyclic ethers, 17, 17t reaction profile, infrared absorbances, 15f Tetrakis(di-isopropylcarbamoyloxy) silane, 125f Thermal reactions, for CO2 conversion, 269–271 Thermolysis, carbamates, 91–92, 91f Thiocarbamoyloxysilanes, resonance structures of, 135s Toluene diisocyanate (TDI), production of, 86, 86f Transesterification reaction, 29–30 organic carbonates Index cyclic carbonate synthesis, 68–70 linear carbonate synthesis, 64–68 Trimethylsilyl aryl ether, 151 TSIL absorbents See Task-specific ionic liquid (TSIL) absorbents U Urea carbamate production routes from CO2, 92–98 derivative synthesis, from amine and CO2, 331–332 BMImCl/CsOH, 332 DBU-promoted synthesis, 332–333, 333s KOH/PEG-promoted synthesis, 332, 333s symmetrical urea, 333, 334s glycerolysis of, 62t Used vs avoided amount, of carbon dioxide, 268–269 UV–vis spectroscopy, of fac-Re(bpy-R) (CO)3X, 177–179, 178f V Value-added chemicals See Catalytic transformation, of carbon dioxide CONTENTS OF PREVIOUS VOLUMES VOLUME 42 Substitution Reactions of Solvated Metal Ions Stephens F Lincoln and Andre´ E Merbach Lewis Acid–Base Behavior in Aqueous Solution: Some Implications for Metal Ions in Biology Robert D Hancock and Arthur E Martell The Synthesis and Structure of Organosilanols Paul D Lickiss Studies of the Soluble Methane Monooxygenase Protein System: Structure, Component Interactions, and Hydroxylation Mechanism Katherine E Liu and Stephen J Lippard Alkyl, Hydride, and Hydroxide Derivatives in the s- and p-Block Elements Supported by Poly(pyrazolyl)borato Ligation: Models for Carbonic Anhydrase, Receptors for Anions, and the Study of Controlled Crystallographic Disorder Gerald Parkin INDEX VOLUME 43 Advances in Thallium Aqueous Solution Chemistry Julius Glaser Catalytic Structure–Function: Relationships in Heme Peroxidases Ann M English and George Tsaprailis Electron-, Energy-, and Atom-Transfer Reactions between Metal Complexes and DNA H Holden Thorp Magnetism of Heterobimetallics: Toward Molecular-Based Magnets Olivier Kahn The Magnetochemistry of Homo- and Hetero-Tetranuclear First-Row d-Block Complexes Keith S Murray Diiron–Oxygen Proteins K Kristoffer Andersson and Astrid Graslund Carbon Dioxide Fixation Catalyzed by Metals Complexes Koji Tanaka INDEX VOLUME 44 Organometallic Complexes of Fullerenes Adam H H Stephens and Malcolm L H Green Group Metal Chalcogenide Cluster Complexes and Their Relationships to Solid-State Cluster Compounds Taro Saito Macrocyclic Chemistry of Nickel Myunghyun Paik Suh Arsenic and Marine Organisms Kevin A Francesconi and John S Edmonds The Biochemical Action of Arsonic Acids Especially as Phosphate Analogues Henry B F Dixon Intrinsic Properties of Zinc(II) Ion Pertinent of Zinc Enzymes Eiicki Kimura and Tbhru Koike 395 396 Activation of Dioxygen by Cobalt Group Metal Complexes Claudio Bianchini and Robert W Zoellner Recent Developments in Chromium Chemistry Donald A House INDEX VOLUME 45 Syntheses, Structures, and Reactions of Binary and Tertiary Thiomolybdate Complexes Containing the (O)Mo(Sx) and (S)Mo(Sx) Functional Groups (x ¼ 1,2,4) Dimitri Coucouvanis The Transition Metal Ion Chemistry of Linked Maerocyclic Ligands Leonard F Lindoy Structure and Properties of Copper-Zinc Superoxide Dismutases Ivano Bertini, Stefano Mangani, and Maria Silvia Viezzoli DNA and RNA Cleavage by Metal Complexes Genevieve Pratviel, Jean Bernadou, and Bernard Meunier Structure-Function Correlations in High Potential Iron Problems J A Cowan and Siu Man Lui The Methylamine Dehydrogenase Electron Transfer Chain C Dennison, G W Canters, S de Vries, E Vijgenboom, and R J van Spanning INDEX VOLUME 46 The Octahedral M6Y6 and M6Y12 Clusters of Group and Transition Metals Nicholas Prokopuk and D F Shriver Contents of Previous Volumes Recent Advances in Noble—Gas Chemistry John H Holloway and Eric G Hope Coming to Grips with Reactive Intermediates Anthony J Downs and Timothy M Greene Toward the Construction of Functional Solid-State Supramolecular Metal Complexes Containing Copper(I) and Silver(I) Megumu Munakata, Liang Ping Wu, and Takayoshi Kuroda-Sowa Manganese Redox opEnzymes and Model Systems: Properties, Structures, and Reactivity Neil A Law, M Tyler Caudle, and Vincent L Pecoraro Calcium-Binding Proteins Bryan E Finn and Torbjoărn Drakenberg Leghemoglobin: Properties and Reactions Michael J, Davies, Christel Mathieu, and Alain Puppo INDEX VOLUME 47 Biological and Synthetic [Fe3S4] Clusters Michael K Johnson, Randall E Duderstadt, and Evert C Duin The Structures of Rieske and Rieske-Type Proteins Thomas A Link Structure, Function, and Biosynthesis of the Metallosulfur Clusters in Nitrogenases Barry E Smith The Search for a “Prismane” Fe-S Protein Alexander F Arendsen and Peter F Lindley NMR Spectra of Iron—Sulfur Proteins Ivano Bertini, Claudio Luchinat, and Antonio Rosato 397 Contents of Previous Volumes Nickel—Iron—Sulfur Active Sites: Hydrogenase and CO Dehydrogenase Juan C Fontecilla-Camps and Stephen W Ragsdale The Cobalt(III)-Promoted Synthesis of Small Peptides Rebecca J Browne, David A Buckingham, Charles R Clark, and Paul A Sutton FeS Centers Involved in Photosynthetic Light Reactions Barbara Schoepp, Myriam Brugna, Evelyne Lebrun, and Wolfgang Nitschke Structures and Reactivities of PlatinumBlues and the Related Amidate-Bridged PlatinumIII Compounds Kazuko Matsumoto and Ken Sakai Simple and Complex Iron–Sulfur Proteins in Sulfate Reducing Bacteria Isabel Moura, Alice S Pereira, Pedro Tavares, and Jose´ J G, Moura INDEX Application of EPR Spectroscopy to the Structural and Functional Study of Iron–Sulfur Proteins Bruno Guigliarelli and Patrick Bertrand The Reactions of Stable Nucleophilic Carbenes with Main Group Compounds Clarie J Carmalt and Alan H Cowley INDEX VOLUME 48 Cumulative Index for Volumes 1-47 VOLUME 49 Inorganic and Bioinorganic Reaction Mechanisms: Application of HighPressure Techniques Rudi van Eldik, Carlos Duăcker-Benfer, and Florian Thaler Substitution Studies of Second- and ThirdRow Transition Metal Oxo Complexes Amdreas Roodt, Amira Abou-Hamdan, Hendrik P Engelbrecht, and Andre E Merbach Protonation, Oligomerization, and Condensation Reactions of Vanadate(V), Molybdate(VI), and Tungstate(VI) J J Cruywagen Medicinal Inorganic Chemistry Zijian Guo and Peter J Sadler VOLUME 50 Group Complexes of P- and As-Donor Ligands Keith Izod Aqueous Solution Chemistry of Beryllium Lucia Alderighi, Peter Gans, Stefano Midollini, and Alberto Vacca Group Element Precursors for the Chemical Vapor Deposition of Electronic Materials Jason S Matthews and William S Rees Jr Molecular, Complex Ionic, and Solid-State PON Compounds Roger Marchand, Wolfgang Schnick, and Norbert Stock Molecular Clusters of Dimetalated Primary Phosphanes and Arsanes Matthias Driess Coordination Complexes of Bismuth(III) Involving Organic Ligands with Pnictogen or Chalcogen Donors Glen G Briand and Neil Burford Phanes Bridged by Group 14 Heavy Elements Hideki Sakurai INDEX 398 VOLUME 51 Clinical Reactivity of the Active Site of Myoglobin Emma Lloyd Raven and A Grant Mauk Enzymology and Structure of Catalases Peter Nicholls, Ignacio Fita, and Peter C Laewen Horseradish Peroxidase Nigel C Veitch and Andrew T Smith Structure and Enzymology of Diheme Enzymes: Cytochrome cdl Nitrate and Cytochrome c Peroxidase Vilmos Fuloăp, Nicholas J Watmough, and Stuart J Ferguson Binding and Transport of Iron-Porphyrins by Hemopexin William T Morgan and Ann Smith Structures of Gas-Generating Heme Enzymes: Nitric Oxide Synthase and Heme Oxygenase Thomas L Poulos, Huiying Li, C S Raman, and David J Schuller The Nitric Oxide-Releasing Heme Proteins from the Saliva of the Blood-Sucking Insect Rhodnius prolixus F Ann Walker and William R Montfort Heme Oxygenase Structure and Mechanism Paul R Ortiz de MonteBano and Angela Wilks De Novo Design and Synthesis of Heme Proteins Brian R Gibney and P Leslie Dutton INDEX VOLUME 52 High-Nuclearity Paramagnetic 3d- Metal Complexes with Oxygen- and Nitrogen-Donor Ligands Richard E P Winpenny Contents of Previous Volumes Transition Metal–Noble Gas Complexes D C Grills and M W George The Materials Chemistry of Alkoxystilbazoles and their Metal Complexes Duncan W Bruce Tetra- and Trinuclear Platinum(II) Cluster Complexes Tadashi Yamaguchi and Tasuku Ito Complexes of Squaric Acid and Its Monosubstituted Derivatives Lincoln A Hall and David J Williams Applications for Polyaza Macrocycles with Nitrogen-Attached Pendant Arms Kevin P Wainwright Perfluorinated Cyclic Phosphazenes Anil J Elias and Jean’ne M Shreeve INDEX VOLUME 53 Wheel-Shaped Polyoxo and Polyoxothiometalates: From the Molecular Level to Nanostructures Anne Dolbecq and Francis Se’cheresse Redox Chemistry and Functionalities of Conjugated Ferrocene Systems Hiroehi Nishihara New Aspects of Metal–Nucleobase Chemistry Andrew Houlton Advances in the Chemistry of Chlorocyclophosphazenes Vadapalli Chandrasekhar and Venkatasubbaiah Krishnan Self-Assembly of Porphyrin Arrays Laura Baldini and Christopher A Hunter INDEX 399 Contents of Previous Volumes VOLUME 54 Solvent Exchange on Metal Ions Frank A Dunand, Lathar Helm, and Andre E Merbach Ligand Substitution Reactions John Burgess and Colin D Hubbard Oxygen Transfer Reactions: Catalysis by Rhenium Compounds James H Espenson Reaction Mechanisms of Nitric Oxide with Biologically Relevant Metal Centers Peter C Ford, Leroy E Laverman and Ivan M Lorkovic Homogeneous Hydrocarbon C–H Bond Activation and Functionalization with Platinum Ulrich Fekl and Karen I Goldberg Density Functional Studies of Iridium Catalyzed Alkane Dehydrogenation Michael B Hall and Hua-Jun Fan Recent Advances in Electron-Transfer Reactions David M Stanbwy Metal Ion Catalyzed Autoxidation Reactions: Kinetics and Mechanisms Istvdn Fabian and Viktor Csordds INDEX VOLUME 55 Dioxygen Activation by Transition Metal Complexes Atom Transfer and Free Radical Chemistry in Aqueous Media Andreja Bakac Redox Reactivity of Coordinated Ligands in Pentacyano(L)Ferrate Complexes Jose´ A Olabe Carbonato Complexes: Models for Carbonic Anhydrase Achyuta N Acharya, Arabinda Das and Anadi C Dash Transition Metal Chemistry of Glucose Oxidase, Horseradish Peroxidase, and Related Enzymes Alexander D Ryabov Properties of Transition Metal Complexes with Metal-Carbon Bonds in Aqueous Solutions as Studied by Pulse Radiolysis Alexandra Masarwa and Dan Meyerstein Transition Metal Complexes with Bis (Hydrazone) Ligands of 2, 6Diacetylpyridine Hepta-Coordination of 3d Metals Ivana Ivanovic´-Burmazovic and Katarina Andjelkovic Potential Applications for the Use of Lanthanide Complexes as Luminescent Biolabels Graham R Motson, Jean S Fleming and Sally Brooker INDEX VOLUME 56 Synergy Between Theory and Experiment as Applied to H/D Exchange Activity Assays in [Fe]H2ase Active Site Models Jesse W Tye, Michael B Hall, Irene P Georgakaki and Marcetta Y Darensbourg Electronic Structure and Spectroscopic Properties of Molybdenum and Tungsten N2, NNH, NNH2, and NNH3 Complexes with Diphosphine Co-Ligands: Insights into the End-on Terminal Reduction Pathway of Dinitrogen Felix Tuczek Quantum Chemical Investigations into the Problem of Biological Nitrogen 400 Fixation: Sellmann-Type Metal–Sulfur Model Complexes Markus Reiher and Bernd A Hess Proton and Electron Transfers in [NiFe] Hydrogenase Per E M Siegbahn Heterolytic Splitting of H-H, Si-H, and Other sigma Bonds on Electrophilic Metal Centers Gregory J Kubas Tetrapodal Pentadentate Nitrogen Ligands: Aspects of Complex Structure and Reactivity Andreas Grohmann Efficient, Ecologically Benign, Aerobic Oxidation of Alcohols Istva´n E Mark, Paul R Giles, Masao Tsukazaki, Isabelle Chelle-Regnaut, Arnaud Gautier, Raphael Dumeunier, Freddi Philippart, Kanae Doda, Jean-Luc Mutonkole, Stephen M Brown and Christopher J Urch Visible Light Photocatalysis by a Titania Transition Metal Complex Horst Kisch, Gerald Burgeih and Wojciech Macyk INDEX Contents of Previous Volumes H NMRD Profiles of Paramagnetic Complexes and Metalloproteins Ivano Bertini, Claudia Luchinat and Giacomo Parigi Gd(III)-Based Contrast Agents for MRI Silvio Aime, Mauro Botta and Enzo Terreno Relaxation by Metal-containing Nanosystems R N Midler, L Vander Elst, A Roch, J A Peters, E Csajbok, P Gillis and Y Gossuin Magnetic Relaxation Dispersion in Porous and Dynamically Heterogeneous Materials Jean-Pierre Korb and Robert G Bryant Water and Proton Exchange Processes on Metal Ions LotharHelm, Gaeălle M, Nicolle and Andre E Merbach Nuclear Magnetic Relaxation Studies on Actinide Ions and Models of Actinide Complexes Jean F Desreux Technical Aspects of fast Field Cycling Gianni Fermnte and Stanislav Sykora INDEX VOLUME 57 VOLUME 58 Introduction: General Theory of Nuclear Relaxation Daniel Canet Diversity-Based Approaches to Selective Biomimetic Oxidation Catalysis Albrecht Berkessel NMR Relaxation in Solution of Paramagnetic Complexes: Recent Theoretical Progress for S Jozef Kowalewski, Danuta Kruk and Giacomo Parigi Selective Conversion of Hydrocarbons with H2O2 Using Biomimetic Non-heme Iron and Manganese Oxidation Catalysts Stefania Tanase and Elisabeth Bouwman 401 Contents of Previous Volumes DNA Oxidation by Copper and Manganese Complexes Marguerite Pitie´, Christophe Boldron and Genevie ‘ve Pratviel Ligand Influences in Copper-Dioxygen Complex-Formation and Substrate Oxidations Lanying Q Hatcher and Kenneth D Karlin Biomimetic Oxidations by Dinuclear and Trinuclear Copper Complexes Giuseppe Battaini, Alessandro Granata, Enrico Monzani, Michele Gullotti and Luigi Casella Green Oxidation of Alcohols using Biominetic Cu Complexes and Cu Enzymes as Catalysts Isabel W.C.E Arends, Patrick Gamez and Roger A Sheldon INDEX Supramolecular Chemistry of Environmentally Relevant Anions Bruce A Moyer, Lætitia H Delmau, Christopher J Fowler, Alexandre Ruas, Debra A Bostick, Jonathan L Sessler, Evgeny Katayev, G Dan Pantos, Jose´ M Llinares, MD Alamgir Hossain, Sung O Kang and Kristin Bowman-James Role of Cation Complexants in the Synthesis of Alkalides and Electrides James L Dye, Mikhail Y Redko, Rui H Huang and James E Jackson Structure-Activity Studies and the Design of Synthetic Superoxide Dismutase (SOD) Mimetics as Therapeutics Dennis P Riley and Otto F Schall Electronic Tuning of the Lability of Inert Co(III) and Pt(II) Complexes Rudi Van Eldik INDEX VOLUME 59 Self-Assembled Metallo-Supramolecular Systems Incorporating b-Diketone Motifs as Structural Elements David J Bray, Jack K Clegg, Leonard F Lindoy and David Schilter Coordination Polymer Open Frameworks Constructed of Macrocyclic Complexes Myunghyun Paik Suh and Hoi Ri Moon Molecular Devices Based on Metallocyclam Subunits Luigi Fabbrizzi, Francesco Foti Maurizio Licchelli, Antonio Poggi, Angelo Taglietti and Miguel Va´zquez Molecular Recognition of Neutral and Charged Guests using Metallomacrocyclic Hosts Ivan V Korendovych, Rebecca A Roesner and Elena V Rybak-Akimova VOLUME 60 Tripodal Carbene and Aryloxide Ligands for Small-Molecule Activation at Electron-Rich Uranium and Transition Metal Centers Karsten Meyer and Suzanne C Bart b-Cyclodextrin-Linked Ru Complexes for Oxidations and Reductions W.-D Woggon, Alain Schlatter and Hao Wang Catalytic Dismutation vs Reversible Binding of Superoxide Ivana Ivanovic’-Burmazovic Tripodal N,N O-Ligands for Metalloenzyme Models and Organometallics Nicolai Burzlaff 402 Hydroxypyranones, Hydroxypyridinones, and their Complexes John Burgess and Maria Rangel Late Transition Metal-Oxo Compounds and Open-Framework Materials that Catalyze Aerobic Oxidations Rui Cao, Jong Woo Han, Travis M Anderson, Daniel A Hillesheim, Kenneth I Hardcastle, Elena Slonkina, Britt Hedman, Keith O Hodgson, Martin L Kirk, Djamaladdin G Musaev, Keiji Morokuma, Yurii V Geletii and Craig L Hill Contents of Previous Volumes Chemistry of Metalated Container Molecules Berthold Kersting and Ulrike Lehmann Mechanistic Considerations on the Reactivity of Green FeIII-TAML Activators of Peroxides Alexander D Ryabov and Terrence J Collins Ligand Exchange Processes on the Smallest Solvated Alkali and Alkaline Earth Metal Cations: An Experimental and Theoretical Approach Ralph Puchta, Ewa Pasgreta and Rudi Van Eldik INDEX VOLUME 61 Controlling Platinum, Ruthenium,and Osmium Reactivity for Anticancer Drug Design Pieter C.A Bruijnincx and Peter J Sadler Design and Function of Metal Complexes as Contrast Agents in MRI Vojteˇch Kubicˇk and Eva To´th Design Considerations Towards Simultaneously Radiolabeled and Fluorescent Imaging Probes Incorporating Metallic Species Sofia I Pascu, Philip A Waghorn, Timothy Conry, Bonita Lin, Catrin James and Jameel M Zayed Spin-State Changes and Reactivity in Transition Metal Chemistry: Reactivity of Iron Tetracarbonyl Maria Besora, Jose´-Luis Carreo´n-Macedo, A´lvaro Cimas and Jeremy N Harvey INDEX VOLUME 62 Molecular Mechanics for Transition Metal Centers: From Coordination Complexes to Metalloproteins Robert J Deeth Calculation of Magnetic Circular Dichroism Spectra With Time-Dependent Density Functional Theory Michael Seth and Tom Ziegler Calcium in Biological Systems John Burgess and Emma Raven Theoretical Investigation of Solvent Effects and Complex Systems: Toward the calculations of bioinorganic systems from ab initio molecular dynamics simulations and static quantum chemistry Marc Bruăssel, Stefan Zahn, E Hey-Hawkins and Barbara Kirchner New Developments in Synthetic Nitrogen Fixation with Molybdenum and Tungsten Phosphine Complexes AmeliDreher,GeraldStephan andFelix Tuczek Simulations of Liquids and Solutions Based on Quantum Mechanical Forces Thomas S Hofer, Bernd M Rode, Andreas B Pribil and Bernhard R Randolf Iron Sequestration by Small Molecules: Thermodynamic and Kinetic Studies of Natural Siderophores and Synthetic Model Compounds Alvin L Crumbliss and James M Harrington 403 Contents of Previous Volumes Spin Interactions in Cluster Chemistry Maren Podewitz and Markus Reiher Inner- and Outer-Sphere Hydrogenation Mechanisms: A Computational Perspective Aleix Comas-Vives, Gregori Ujaque and Agustı´ Lledo´s Computational Studies on Properties, Formation, and Complexation of M(II)-Porphyrins Tatyana E Shubina Dealing with Complexity in Open-Shell Transition Metal Chemistry from a Theoretical Perspective: Reaction Pathways, Bonding, Spectroscopy, and Magnetic Properties Frank Neese, William Ames, Gemma Christian, Mario Kampa, Dimitrios G Liakos, Dimitrios A Pantazis, Michael Roemelt, Panida Surawatanawong and Shengfaye Vibronic Coupling in Inorganic Systems: Photochemistry, Conical Intersections, and the Jahn–Teller and Pseudo-Jahn– Teller Effects Russell G Mckinlay, Justyna M Z˙urek and Martin J Paterson Elementary Reactions in Polynuclear Ions and Aqueous–Mineral Interfaces: A New Geology James R Rustad The Aromatic Amino Acid Hydroxylase Mechanism: A Perspective from Computational Chemistry Elaine Olsson, Knut Teigen, Aurora Martinez and Vidar R Jensen Photophysics of Soft and Hard Molecular Assemblies Based on Luminescent Complexes Cristian A Strassert, Matteo Mauro and Luisa De Cola Photochemistry and Photophysics of Metal Complexes with Dendritic Ligands Vincenzo Balzani, Giacomo Bergamini and Paola Ceroni Photochemistry and Photocatalysis of Rhenium(I) Diimine Complexes Hiroyuki Takeda, Kazuhide Koike, Tatsuki Mrimoto, Hiroki Inumaru and Osamu Ishitani Design of Porphyrin-Based Photosensitizers for Photodynamic Therapy Luis G Arnaut Photosensitization and Photocatalysis in Bioinorganic, Bio-Organometallic and Biomimetic Systems Guănther Knoăr and Uwe Monkowius Transition Metal Complexes as Solar Photocatalysts in the Environment: A Short Review of Recent Development Zofia Stasicka Photochemical Activation and Splitting of H2O, CO2, and N2 Induced by CT Excitation of Redoxactive Metal Complexes Arnd Vogler and Horst Kunkely Visible Light Photocatalysis by Metal Halide Complexes Containing Titania as a Semiconductor Ligand Horst Kisch INDEX VOLUME 63 Luminescent Lanthanide Sensors Morgan L Cable, Dana J Levine, James P Kirby, Harry B Gray and Adrian Ponce Photocatalysis by Inorganic Solid Materials: Revisiting its Definition, Concepts, and Experimental Procedures B Ohtani INDEX 404 VOLUME 64 Predictive Studies of Oxygen Atom Transfer Reactions by Compound I of Cytochrome P450: Aliphatic and Aromatic Hydroxylation, Epoxidation, and Sulfoxidation Sam P De Visser Heme-Containing Dioxygenases Igor Efimov, Jaswir Basran, Sarah J Thackray, Sandeep Handa, Christopher G Mowat and Emma Lloyd Raven Reactivity of Manganese Superoxide Dismutase Mimics Toward Superoxide and Nitric Oxide: Selectivity Versus Cross-Reactivity Ivana Ivanovic-Burmazovic and Milos R Filipovic Azanone (HNO) Interaction with Hemeproteins and Metalloporphyrins Fabio Doctorovich, Damian E Bikiel, Juan Pellegrino, Sebastia´n A Sua´rez and Marcelo A Martı´ Advances in the Mechanistic Understanding of Selected Reactions of Transition Metal Polyaminecarboxylate Complexes Ariane Brausam and Rudi van Eldik Polyaminecarboxylateruthenium(III) Complexes on the Mosaic of Bioinorganic Reactions Kinetic and Mechanistic Impact Debabrata Chatterjee and Rudi van Eldik The Chemistry of Monovalent Copper in Aqueous Solutions Ariela Burg and Dan Meyerstein Contents of Previous Volumes Hypothiocyanite Michael T Ashby INDEX VOLUME 65 Homogeneous Multicopper Catalysts for Oxidation and Hydrocarboxylation of Alkanes Alexander M Kirillov, Marina V Kirillova, and Armando J.L Pombeiro Homogeneous Catalytic Olefin Epoxidation with Molybdenum Complexes Christina Muăller, Nidhi Grover, Mirza Cokoja, and Fritz E Kuăhn Manganese and Iron Bleaching and Oxidation Catalysts Ronald Hage, Johannes W de Boer, Fabien Gaulard, and Karin Maaijen Green Challenges of Catalysis via Iron(IV) oxo and Iron(V)oxo Species Alexander D Ryabov Manganese Compounds as Versatile Catalysts for the Oxidative Degradation of Organic Dyes Sabine Rothbart and Rudi van Eldik Catalysis or Convenience? Perborate in Context John Burgess and Colin D Hubbard INDEX ... devoted to CO2 chemistry, co- edited by Michele Aresta from the University of Bari, Italy At the recent 4th EuCheMS Chemistry Congress in Prague, August 2012, a special symposium on CO2 chemistry. .. bifunctional (salen )Co( III) catalyst containing bulky substituents (complex 5), Lu and coworkers have synthesized a stereoselective copolymer from racepichlorohydrin and CO2 with a krel of 8.9... temperature, with concomitant faster rate, while still maintaining copolymer selectivity BLOCK COPOLYMERS OF POLYCARBONATES AND LACTIDES As noted earlier, the copolymer afforded from the coupling of