CO Chemistry

406 Pages·2014·19.42 MB·English

by  Michele Aresta and Rudi van Eldik (Eds.)

ADVISORY BOARD
L. H. Gade D. Darensbourg
UniversitätHeidelberg TexasA&MUniversity
Germany CollegeStation,Texas,USA
M. L. H. Green H. B. Gray
UniversityofOxford CaliforniaInstituteofTechnology
Oxford,UnitedKingdom Pasadena,California,USA
A. E. Merbach P. A. Lay
LaboratoiredeChimieetBioanorganiqueEFPL, UniversityofSydney
Lausanne,Switzerland Sydney,Australia
P. J. Sadler J. Reedijk
UniversityofWarwick LeidenUniversity
Warwick,England Leiden,TheNetherlands
K. Wieghardt Y. Sasaki
Max-Planck-Institut HokkaidoUniversity
Mülheim,Germany Sapporo,Japan
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CONTRIBUTORS
AntonellaAngelini
DepartmentofChemistry,UniversityofBari,Bari,Italy
MicheleAresta
CIRCCViaCelsoUlpiani27,Bari,Italy
ArnoBehr
TechnicalChemistry,DepartmentofBio-andChemicalEngineering,TechnicalUniversity
ofDortmund,Dortmund,Germany
RobertH.Carr
Huntsman(Europe)bvba,Kortenberg,Belgium
DonaldJ.Darensbourg
DepartmentofChemistry,TexasA&MUniversity,CollegeStation,Texas,USA
Zhen-FengDiao
StateKeyLaboratoryandInstituteofElemento-OrganicChemistry,NankaiUniversity,
Tianjin,P.R.China
AngelaDibenedetto
CIRCCViaCelsoUlpiani27,andDepartmentofChemistry,UniversityofBari,Bari,Italy
EtsukoFujita
ChemistryDepartment,BrookhavenNationalLaboratory,Upton,NewYork,USA
KyleA.Grice
DepartmentofChemistryandBiochemistry,UniversityofCalifornia,SanDiego,LaJolla,
California,USA
Liang-NianHe
StateKeyLaboratoryandInstituteofElemento-OrganicChemistry,NankaiUniversity,
Tianjin,P.R.China
RichardH.Heyn
SINTEFMaterialsandChemistry,Blindern,Oslo,Norway
YuichiroHimeda
NationalInstituteofAdvancedIndustrialScienceandTechnology,Tsukuba,Ibaraki,and
JapanScienceandTechnologyAgency,Kawaguchi,Saitama,Japan
IvoJacobs
HuntsmanHollandBV,Rotterdam,TheNetherlands
KonstantinKraushaar
Institutfu¨rAnorganischeChemie,ArbeitsgruppeSiliciumchemieundChemische
Materialwissenschaft,TechnischeUniversita¨tBergakademieFreiberg,Freiberg,Germany
ix
x Contributors
EdwinKroke
Institutfu¨rAnorganischeChemie,ArbeitsgruppeSiliciumchemieundChemische
Materialwissenschaft,TechnischeUniversita¨tBergakademieFreiberg,Freiberg,Germany
CliffordP.Kubiak
DepartmentofChemistryandBiochemistry,UniversityofCalifornia,SanDiego,LaJolla,
California,USA
Yu-NongLi
StateKeyLaboratoryandInstituteofElemento-OrganicChemistry,NankaiUniversity,
Tianjin,P.R.China
Hannu-PetteriMattila
ThermalandFlowEngineeringLaboratory,A˚boAkademiUniversity,Turku,Finland
JamesT.Muckerman
ChemistryDepartment,BrookhavenNationalLaboratory,Upton,NewYork,USA
KristinaNowakowski
TechnicalChemistry,DepartmentofBio-andChemicalEngineering,TechnicalUniversity
ofDortmund,Dortmund,Germany
DanaSchmidt
Institutfu¨rAnorganischeChemie,ArbeitsgruppeSiliciumchemieundChemische
Materialwissenschaft,TechnischeUniversita¨tBergakademieFreiberg,Freiberg,Germany
AnkeSchwarzer
Institutfu¨rAnorganischeChemie,ArbeitsgruppeSiliciumchemieundChemische
Materialwissenschaft,TechnischeUniversita¨tBergakademieFreiberg,Freiberg,Germany
Wan-HuiWang
NationalInstituteofAdvancedIndustrialScienceandTechnology,Tsukuba,Ibaraki,and
JapanScienceandTechnologyAgency,Kawaguchi,Saitama,Japan
Zhen-ZhenYang
StateKeyLaboratoryandInstituteofElemento-OrganicChemistry,NankaiUniversity,
Tianjin,P.R.China
RonZevenhoven
ThermalandFlowEngineeringLaboratory,A˚boAkademiUniversity,Turku,Finland
PREFACE
Volume66ofAdvancesinInorganicChemistryisathematicvolumedevotedto
CO chemistry, co-edited by Michele Aresta from the University of Bari,
2
Italy. At the recent 4th EuCheMS Chemistry Congress in Prague, August
2012, a special symposium on CO chemistry was organized as part of
2
the Inorganic Chemistry Program. Understanding the important industrial
and environmental role of CO effluents is a multidisciplinary challenge to
2
scientists working on various aspects of CO chemistry with the ambitious
2
targetofconvertinglargevolumesofCO foraneffectivecarbonrecycling.
2
Should the latter be implemented, it would result in a significant environ-
mental benefit with fossil reserves preservation for future generations.
Anumberofspeakersatthissymposiumandotherleadingscientistsworking
inthisareawereinvitedtocontributetothisspecialissue.Thecontributed
chapters cover an important part of CO utilization strategies.
2
In the opening chapter, Donald J. Darensbourg presents a personal
account on his adventures in the synthesis of copolymers from CO and
2
cyclic ethers. This is followed by a chapter on the synthesis of organic car-
bonates by Angela Dibenedetto and Antonella Angelini. In Chapter 3,
Richard H. Heyn, Ivo Jacobs, and Robert H. Carr report on the synthesis
ofaromaticcarbamatesfromCO andtheimplicationsforthepolyurethane
2
industry. This is followed by a chapter on the reactions of CO and CO
2 2
analogs with reagents containing Si–H and Si–N units reported by
KonstantinKraushaar,DanaSchmidt,AnkeSchwarzer,andEdwinKroke.
InChapter5,KyleA.GriceandCliffordP.Kubiakreportonrecentstudies
of rhenium and manganese bipyridine carbonyl catalysts for the electro-
chemical reduction of CO . In the subsequent chapter, Wan-Hui Wang,
2
Yuichiro Himeda, James T. Muckerman, and Etsuko Fujita discuss the
interconversionofCO /H andformicacidundermildconditionsinwater
2 2
andfocusonliganddesignforeffectivecatalysis.Chapter7isdevotedtothe
catalytic hydrogenation of CO to formic acid by Arno Behr and Kristina
2
Nowakowski.This is followed by a report on theconversion of “exhaust”
carboninto“working”carbonbyMicheleAresta,AngelaDibenedetto,and
Antonella Angelini. In Chapter 9, Yu-Nong Li, Liang-Nian He, Zhen-
Feng Diao, andZhen-Zhen Yang present areport on carbon capturewith
simultaneous activation and subsequent transformation. In the final contri-
bution,Hannu-PetteriMattilaandRonZevenhovenpresentanaccounton
xi
xii Preface
the production of precipitated calcium carbonate from steel converter slag
and other calcium-containing industrial wastes and residues.
Wearemostappreciativeoftheeffortsoftheauthorsandtheircolleagues
whohaveprovidedinformative,instructive,andauthoritativecontributions
forthisthematicvolume.WebelieveresearchersinthefieldofCO chem-
2
istry 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-Nu¨rnberg, Erlangen, Germany
October 2013
CHAPTER ONE
Personal Adventures in the
Synthesis of Copolymers from
Carbon Dioxide and Cyclic Ethers
Donald J. Darensbourg
DepartmentofChemistry,TexasA&MUniversity,CollegeStation,Texas,USA
Contents
1. Introduction 1
2. CarbonDioxideasaSourceofChemicalCarbon 3
3. CopolymersfromOxiranesandCarbonDioxide 4
4. BlockCopolymersofPolycarbonatesandLactides 12
5. TerpolymersfromOxiranesandCarbonDioxide 13
6. DepolymerizationofPolycarbonates 19
Acknowledgments 22
References 22
Abstract
Thischapterfocusesonrecentadvancesinthedevelopmentofwell-definedmetalcat-
alystsforthecouplingofCO andoxiranesfortheproductionofpolycarbonatesand
2
cyclic carbonates. Since this subject has been comprehensively covered in several
reviewsrecently,thistreatmentwillcenteroncontributionsfromourlaboratorywithin
thecontextofotherpublishedwork.Specialattentionwillbegiventoourcurrentstud-
ies dealing with depolymerization pathways of polymeric materials derived from
completelyalternatingcopolymerizationofCO andepoxides.
2
Keywords: Carbon dioxide, Copolymerization, Terpolymerization, Epoxides,
Metal catalysts, Polycarbonates,Salen ligands
1. INTRODUCTION
Theinterestofmyresearchprogramintheorganometallicchemistry
ofcarbondioxidebeganinthemid-1970swhenwewereinvestigatingthe
mechanistic aspects of group 6 metal carbonyl-catalyzed water–gas shift
reactions.Thesestudieseventuallyledustoexaminingindetailtheinsertion
AdvancesinInorganicChemistry,Volume66 #2014ElsevierInc. 1
ISSN0898-8838 Allrightsreserved.
http://dx.doi.org/10.1016/B978-0-12-420221-4.00001-9
2 DonaldJ.Darensbourg
reactionsofCO intoMdOHandMdOR(R¼alkyloraryl)bonds.We
2
and others definitively established that insertion of CO into metaldOR
2
bonds occurred in the absence of prior coordination of CO to the metal
2
center (1, 2). That is, the major interaction in the transition state (TS)
involves the electrophilic carbon center of CO with a lone pair on the
2
nucleophilicoxygenatomoftheORgroupasdepictedinFigure1.1.Con-
sistentwith thisinterpretation,therateofthisreactionishighlydependent
onthenucleophilicityofthemetalalkoxidemoietysinceCO issuchapoor
2
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 CO .
2
The reaction described in Figure 1.1 is one of the pivotal steps in the
couplingofCO andepoxidestoprovidepolycarbonatesandcycliccarbon-
2
ates(seeEquation1.1).Thisisparticularlyrelevantsincethemostprominent
metal catalysts for this process, for example, (salen)CrCl
(salen¼salicylaldimine), upon binding the growing polymer chain, are
coordinatively saturated. In this chapter, I will describe our most recent
advancesinthedevelopmentofwell-definedmetalcatalystsforthecoupling
reactions of CO and cyclic ethers (oxiranes) for the production of poly-
2
carbonates or cyclic carbonates. These studies will focus on contributions
fromourlaboratorywithinthecontextofotherpublishedwork.Thissub-
jectmatterhasbeencomprehensivelycoveredinnumerousreviews,includ-
ingonewhichchronologicallydescribeddevelopmentsinthisfieldstarting
withthepioneeringeffortsofInoueandcoworkers(3).Priortosummariz-
ingourrecentresultsontheutilizationofCO toproducepolymericmate-
2
rials, it is useful to assess the issues surrounding the use of CO in organic
2
synthesis.
O
O
O + CO metal catalyst O + O O ð1:1Þ
2 O
n
polycarbonate cyclic carbonate
d-
O O
C O
d+ C
[M] OR + CO2 [M] O [M] O OR
R
Figure1.1 CarbondioxideinsertionpathwayintometaldORbond.
PersonalAdventuresintheSynthesisofCopolymersfromCO 3
2
2. 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
foritsrecovery,albeitoftenwithanegativeenvironmentalimpact.Never-
theless,ifwecontinuetoconsumethisfinitesourceofprereducedcarbonin
particularasfuels,concomitantlyemittingtheoxidizedcarbontotheatmo-
sphere, we not only will lead to climate change but also will exhaust this
sourceof chemicalcarbon.This situationclearlydoes notsatisfytheEPA’s
definitionofsustainability,thatis,“meetingtheneedsofthepresentwithout
compromisingtheabilityoffuturegenerationstomeettheirownneeds.”At
thispoint,theonlyreservoirsofcarbonforchemicalsynthesiswillbeimme-
diatebiomassandcarbondioxide.Ofcourse,coupledwiththisoccurrenceisthe
factthattheworldpopulationisprojectedtoincreaseby50%by2044to9
billion,alongwithanincreaseintheeconomiesofthisemergingpopulation
growth.
The current uses of CO for chemical synthesis are quite limited, with
2
the major industrial processes being the synthesis of urea, salicylic acid,
methanol, and inorganic carbonates (4). More recently, a sizable quantity
of CO is utilized in a greener synthesis of BPA-derived polycarbonate,
2
whichavoidstheuseoftheverytoxicphosgenereagent(seeEquation1.2).
Thatis,AsahiKaseiCorporationhassolvedtheengineeringproblemsasso-
ciated with the disfavored equilibria involved in the synthesis of diphenyl
carbonatefromdimethylcarbonateviaethylenecarbonate,thelatterreagent
beingreadilysynthesizedfromethyleneoxideandCO (5).Ofimportance,
2
thecoproductinthisreaction,ethyleneglycol,isacommoditychemicalthat
isgenerallyproducedbyhydrationofethyleneoxide.Allotherreagentsare
recycled in the process (see Figure 1.2):
O
O
melt
nPhO PhO + n HO OH O O C + 2n PhOH
n
ð1:2Þ
Thelargestobstacleforestablishingindustrialprocessesbasedontheuse
of CO as a raw material is the high energy required to transform CO
2 2
because of its low-energy level. Hence, processes involving nonrenewable
sources of energy require the use of high-energy starting materials.
4 DonaldJ.Darensbourg
O
PhO OPh
bis-phenol A
PhOH
BPA polycarbonate
O
O
CO2 + O O O MeOH MeO OMe + HOCH2CH2OH
DMC Ethylene glycol
Figure1.2 AsahiKasei’snonphosgeneroutetoBPApolycarbonate,productsinredand
recyclablesingreen.
The reaction described in Equation (1.1) fits this requirement, being based
on small-membered ring compounds and affording oxidized low-energy
synthetic targets.
3. COPOLYMERS FROM OXIRANES AND CARBON
DIOXIDE
Our initial reportutilizing binary (salen)CrCl catalyst systemsfor the
copolymerization of cyclohexene oxide or propylene oxide and carbon
dioxide providedthestimulus for thedevelopment of the most productive
andselectivecatalystscurrentlystudied(6,7).Thatis,theuseofthesecom-
plexes and their cobalt(III) and aluminum(III) analogs, and their closely
related porphyrin derivatives, has dominated studies leading to effective
copolymerization processes of CO with a variety of epoxides (3). This
2
chemistryhasevolvedtothepointtodaythatmostactiveandselectivecat-
alyst systems are composed of bifunctional catalysts where the cocatalyst is
covalently attached to the salen ligand (8–10).
Scheme1.1 summarizes theaccepted modeof reaction of these catalyst
systems, where the cocatalyst is an onium salt composed of various anion
initiators.Itisnoteworthytorecallfromourearlierstudiesinorganometallic
chemistrythattheCO insertionstepdoesnotrequirepriorcoordinationof
2
CO to the coordinatively saturated metal center. Additionally, at modest
2
CO pressures where insertion of CO is not rate-limiting, the slow step
2 2
isproposedtoinvolvering-openingofaboundepoxidesubstratebythecar-
bonate end group of the growing polymer chain. The more detailed path-
waysforproductionofthethermodynamicallystablefive-memberedcyclic
carbonateareillustratedinScheme1.2.Inourearlystudy,weclearlydem-
onstrated that employingthe(salen)CrCl catalyst system, the selectivityfor