Table Of ContentTopics in Organometallic Chemistry 53
Xiao-Bing Lu Editor
Carbon
Dioxide and
Organometallics
53
Topics in Organometallic Chemistry
Editorial Board
M. Beller, Rostock, Germany
J.M. Brown, Oxford, United Kingdom
P.H. Dixneuf, Rennes CX, France
J. Dupont, Porto Alegre, Brazil
A. Fu¨rstner, Mu¨lheim, Germany
Frank Glorius, Mu¨nster, Germany
L.J. Gooßen, Kaiserslautern, Germany
T. Ikariya, Tokyo, Japan
S. Nolan, St Andrews, United Kingdom
Jun Okuda, Aachen, Germany
L.A. Oro, Zaragoza, Spain
Q.-L. Zhou, Tianjin, China
Aims and Scope
TheseriesTopicsinOrganometallicChemistrypresentscriticaloverviewsofresearch
resultsinorganometallicchemistry.Asourunderstandingoforganometallicstructure,
properties and mechanisms increases, new ways are opened for the design of
organometalliccompoundsandreactionstailoredtotheneedsofsuchdiverseareasas
organicsynthesis,medicalresearch,biologyandmaterialsscience.Thusthescopeof
coverage includes a broad range of topics of pure and applied organometallic
chemistry,wherenewbreakthroughsarebeingachievedthatareofsignificancetoa
largerscientificaudience.
TheindividualvolumesofTopicsinOrganometallicChemistryarethematic.Review
articles are generally invited by the volume editors. All chapters from Topics
in Organometallic Chemistry are published OnlineFirst with an individual DOI.
Inreferences,TopicsinOrganometallicChemistryisabbreviatedasTopOrganomet
Chemandcitedasajournal.
Moreinformationaboutthisseriesathttp://www.springer.com/series/3418
Xiao-Bing Lu
Editor
Carbon Dioxide and
Organometallics
With contributions by
(cid:1) (cid:1) (cid:1) (cid:1)
A. Angelini M. Aresta M. Beller M. Brill
(cid:1) (cid:1) (cid:1) (cid:1)
L.P. Carrodeguas C.S.J. Cazin L.-N. He R. Jackstell
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
A.W. Kleij S. Kraus V. Laserna F. Lazreg Q. Liu
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
X.-B. Lu R. Ma S.P. Nolan B. Rieger J. Rintjema
(cid:1) (cid:1) ~ (cid:1) (cid:1)
C. Romain P.K. Saini S. Sopena A. Thevenon
(cid:1) (cid:1) (cid:1)
C.K. Williams L. Wu S. Zhang W.-Z. Zhang
Editor
Xiao-BingLu
StateKeyLaboratoryofFineChemicals
DalianUniversityofTechnology
Dalian
China
ISSN1436-6002 ISSN1616-8534 (electronic)
TopicsinOrganometallicChemistry
ISBN978-3-319-22077-2 ISBN978-3-319-22078-9 (eBook)
DOI10.1007/978-3-319-22078-9
LibraryofCongressControlNumber:2015949229
SpringerChamHeidelbergNewYorkDordrechtLondon
©SpringerInternationalPublishingSwitzerland2016
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Preface
Atmospheric carbon dioxide is the elixir of life. It is the primary raw material
for green plants to construct their tissues through photosynthesis, which in turn
are the feedstocks for animals to build theirs. The managed ecosystems maintain
the quality of life and the environment for millions years. Nevertheless, human
activities in the recent two centuries significantly disturb the carbon cycle of our
planet, which involves dynamic carbon exchanges between the geosphere, the
biosphere, the oceans and the atmosphere. It was observed that carbon dioxide
concentrations in the atmosphere have been increasing significantly over the past
century, especially with an average growth of 2 ppm/year in the last 10 years.
Compared to the rather steady level of the pre-industrial era (about 280 ppm),
the concentration of atmospheric carbon dioxide in 2013 (396 ppm) was about
40%higherthanthatinthemid-1800s.
Absolutely, mitigating climate change, preserving the environment, replacing
fossilfuelsandusingrenewableenergyarethegreatchallengesforoursustainable
planet. The utilization of carbon dioxide as a C1 feedstock for producing fuels
and chemicals is an attractive strategy to fulfill these grand challenges. Reusing
CO not only addresses the balance of CO in the atmosphere, but also employs
2 2
it as an alternative feedstock to fossil fuels, an abundant, inexpensive and
non-toxicrenewablecarbonsource.Asalonger-termvisionaryidea,itispossible
tocreateaCO -economyforachievingfull-circlerecyclingofCO asarenewable
2 2
energysource,analogoustoplants’convertingCO andwatertosugarandO via
2 2
photosynthesis. Therefore, the development of efficient catalytic processes for
carbon dioxide transformation into desirable, economically competitive products
has been a long-standing goal for chemists. Up to now, more than 20 reactions
involving CO as a starting material have been developed in recent decades.
2
Althoughthenumberremainsless,severalCO reactionsthatincludethesyntheses
2
of urea, methanol, salicylic acid, synthetic gas and organic carbonates have been
successfully industrialized. It is apparent that the quantity of consumed CO in
2
these processes is likely a very small fraction (0.5%) of the total CO generated
2
from human activity (about 37 Gt). However, these strategies potentially provide
v
vi Preface
moreenvironmentallybenignroutestoproducingchemicalsotherwisemadefrom
thereagentsdetrimentaltotheenvironment.
Carbondioxideisathermodynamicallystablemolecule(ΔG(cid:3)¼(cid:4)396kJ/mol),
f
the end product in any carbon-based combustion process, thus relatively high-
energy reagents are often used to facilitate its transformation. From the energetic
pointofview,theconversionofCO willrequireanamountofenergythatdepends
2
onthedownwardstepsoftheoxidationstateofcarbonfrom+4inCO tothevalue
2
in the target chemical. If one converts CO into species in which the O/C ratio is
2
lessthan2,energyisneeded.Conversely,ifCO iskeptinits+4oxidationstateby
2
increasingtheO:Cratiointheproductsderivedfromit,thetransformationprocess
is an exoenergic reaction (e.g. production of organic carbonates). However,
whether endothermic or exoenergic reaction, the activation of carbon dioxide is
pivotal for its effective transformation. In recent decades, we have witnessed the
great progress in carbon dioxide activation and catalytic transformation. Among
these processes, organometallics plays an important role in activating CO . This
2
volume (Carbon Dioxide and Organometallics) is a timely overview of various
reactionsutilizingcarbondioxideasastartingmaterial,focusedonmetal-mediated
incorporationofCO .Severalexcellentandactiveresearchgroupsinthisfieldare
2
invited to highlight new directions and developments in the exciting field of CO
2
activationandtransformation.
This volume is organized into nine chapters, which are independent of each
other, and the authors responsible for each chapter were given sufficient freedom
to organize their materials. As a consequence, the possible overlapped citation
and description of some literatures are inevitable; however, these reiterations
should be different based on their individual viewpoints. The first chapter
by Prof. Aresta provides an introduction to the structural features of carbon
dioxide molecule and its interaction with electrophiles and nucleophiles. Chapter
“Metal Complexes Catalyzed Cyclization with CO ” by Prof. Kleij describes
2
organometallic/inorganic complexes catalyzed cyclization reactions that incorpo-
rate an intact CO fragment without changing the formal oxidation state
2
of the carbon centre. Chapter “Silver-Catalyzed Carboxylation Reaction Using
Carbon Dioxide as Carboxylative Reagent” by Dr. Zhang covers silver-catalyzed
carboxylation reactions using carbon dioxide as a carboxylative reagent. In
this chapter, silver-catalyzed cyclization reactions of propargylic alcohols or
amines, o-alkynylanilines and alkynyl ketones with carbon dioxide, as well as
carboxylation of terminal alkynes and arylboronic esters with carbon dioxide will
be documented. The copolymerization of carbon dioxide and epoxides represents
an interesting method to prepare a range of aliphatic polycarbonates. In chapter
“Dinuclear Metal Complex-Mediated Formation of CO -Based Polycarbonates”,
2
Prof. Williams highlights kinetic and mechanistic studies which have implicated
di- or multi-metallic pathways for CO /epoxide polymerization catalysis and
2
the subsequent development of highly active and selective di(multi-) nuclear
catalysts. Chapter “Transition Metal-Free Incorporation of CO ” by Prof. He
2
features recent advances on methodologies for catalytic transformation of CO
2
promoted by organocatalysts (e.g. N-heterocyclic carbenes, frustrated Lewis pairs
Preface vii
and superbases), ionic liquids, main-group metals to produce value-added
chemicals. Chapter “CO -Mediated Formation of Chiral Fine Chemicals” by
2
Prof. Lu aims to principally showcase the recent progress regarding the
stereochemically controlled catalytic CO fixation/conversion processes for the
2
production of CO -based chiral fine chemicals. Chapter “Ni-Catalyzed Synthesis
2
of Acrylic Acid Derivatives from CO and Ethylene” by Prof. Rieger focuses
2
thediscussionontheanalysisofthereactionmechanismofNi-catalyzedsynthesis
of acrylic acid derivatives from CO and ethylene. Chapter “Transition Metal-
2
Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide” by Prof.
Nolanprovidesacomprehensivesummaryontransitionmetal-catalyzedcarboxyl-
ationreactionsinvolvingtheuseofCO inorganicsynthesisanditsincorporation
2
into typical organic substrates such as alkenes, alkynes and various C(cid:4)H and
C–heteroatom bonds. In chapter “Recent Progress in Carbon Dioxide Reduction
Using Homogeneous Catalysts”, Prof. Beller and coworkers describe the
recent developments in carbon dioxide reductions to CO, formic acid derivatives,
methanolandmethylamines,mainlyfocusingontheuseofdefinedorganometallic
catalysts.
Theeditorbelievesthattheauthorshavehighlightedthemostimportantprogress
with regard to carbon dioxide activation and transformation in recent decades.
This volume is expected to serve as a guide for researchers with an interest
in catalytic CO fixation/conversion. The descriptive modes for carbon dioxide
2
activationinthisvolumebenefitforencouragingthereadersmorecreativeideasfor
thedevelopmentofnewreactionswithCO asaC1feedstock.
2
The editor is very grateful to all chapter authors for their significant contri-
butionstothevolume.SpecialthanksgotoDr.ElizabethHawkins,whooriginally
initiated this book, and to Arun Manoj for his patience and support during the
editingprocess.
Dalian,China Xiao-BingLu
ThiSisaFMBlankPage
Contents
TheCarbonDioxideMoleculeandtheEffectsofItsInteraction
withElectrophilesandNucleophiles. . . . . . . . . . . . . . . . . . . . . . . . . . . 1
MicheleArestaandAntonellaAngelini
MetalComplexesCatalyzedCyclizationwithCO . . . . . . . . . . . . . . . . 39
2
JeroenRintjema,LeticiaPe~naCarrodeguas,VictorLaserna,
SergioSope~na,andArjanW.Kleij
Silver-CatalyzedCarboxylationReactionUsingCarbonDioxide
asCarboxylativeReagent. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . 73
Wen-ZhenZhang
DinuclearMetalComplex-MediatedFormationofCO -Based
2
Polycarbonates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
CharlesRomain,ArnaudThevenon,PrabhjotK.Saini,
andCharlotteK.Williams
TransitionMetal-FreeIncorporationofCO . . . . . . . . . . . . . . . . . . . . 143
2
ShuaiZhang,RanMa,andLiang-NianHe
CO -MediatedFormationofChiralFineChemicals. . . . . . . . . . . . . . 171
2
Xiao-BingLu
Ni-CatalyzedSynthesisofAcrylicAcidDerivativesfromCO
2
andEthylene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
SebastianKrausandBernhardRieger
TransitionMetal-CatalyzedCarboxylationofOrganicSubstrates
withCarbonDioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
MarcelBrill,Fa¨ımaLazreg,CatherineS.J.Cazin,andStevenP.Nolan
ix
