Table Of ContentCOMPREHENSIVE
ORGANOMETALLIC
CHEMISTRY IV
COMPREHENSIVE
ORGANOMETALLIC
CHEMISTRY IV
EDITORS-IN-CHIEF
GERARD PARKIN
Department of Chemistry, Columbia University, New York, NY, United States
KARSTEN MEYER
Department of Chemistry and Pharmacy, Friedrich-Alexander-Universität, Erlangen, Germany
DERMOT O’HARE
Department of Chemistry, University of Oxford, Oxford, United Kingdom
VOLUME 3
GROUPS 3 TO 4 AND THE f ELEMENTS - PART 1
VOLUME EDITORS
DAVID P. MILLS
STEPHEN T. LIDDLE
Department of Chemistry, The University of Manchester, Manchester, United Kingdom
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CONTENTS OF VOLUME 3
EditorBiographies vii
ContributorstoVolume3 xiii
Preface xv
3.01 IntroductiontoGroups3to4andthef-Elements 1
DavidPMillsandStephenTLiddle
3.02 Alkyl,carbonylandcyanidecomplexesofthegroup3metalsandlanthanides 3
KeithIzod
3.03 Hydride,Alkyl,Aryl,Acetylide,Carbonyl,andCyanideComplexesoftheActinides 58
TrevorWHayton
3.04 Alkyl,CarbonylandCyanideComplexesoftheGroup4Metals 85
BenjaminDWard,OwaenGGuppy,andMatthewSShaw
3.05 N-HeterocyclicandAbnormal/MesoionicCarbeneComplexesoftheGroup3Metals
andLanthanides 163
FlorianJaroschik
3.06 N-HeterocyclicandMesoionicCarbeneComplexesoftheActinides 201
StephanHohlochandJamesRPankhurst
3.07 N-HeterocyclicandMesoionicCarbeneComplexesoftheGroup4Metals 227
AdrienTNormand
3.08 AlkylideneComplexesoftheGroup3MetalsandLanthanides 268
MatthewPStevensandFabrizioOrtu
3.09 ActinideMetalCarbeneComplexes:Synthesis,StructureandReactivity 312
ErliLu
3.10 AlkylideneComplexesoftheGroup4TransitionMetals 347
DanielJMindiola,JRolandoAguilar-Calderón,andPavelZatsepin
3.11 AlkenesandAllylComplexesoftheGroup3MetalsandLanthanides 382
MaximeBeauvois,YohanChampouret,FannyBonnet,andMarcVisseaux
3.12 Alkene,AlkyneandAllylComplexesoftheActinides 449
MarcDWalter
3.13 Group4MetalAlkyne,Alkene,andAllylComplexes 477
HayatoTsurugi
v
EDITOR BIOGRAPHIES
Editors in Chief
KarstenMeyerstudiedchemistryattheRuhrUniversityBochumandperformed
his Ph.D. thesis work on the molecular and electronic structure of first-row
transition metal complexes under the direction of Professor Karl Wieghardt at
the Max Planck Institute in Mülheim/Ruhr (Germany). He then proceeded to
gainresearchexperienceinthelaboratoryofProfessorChristopherCumminsat
theMassachusettsInstituteofTechnology(USA),whereheappreciatedtheartof
synthesisanddevelopedhispassionforthecoordinationchemistryandreactivity
ofuraniumcomplexes.In2001,hewasappointedtotheUniversityofCalifornia,
SanDiego,asanassistantprofessorandwasnamedanAlfredP.SloanFellowin
2004. In 2006, he accepted an offer (C4/W3) to be the chair of the Institute of
Inorganic & General Chemistry at the Friedrich-Alexander-University Erlangen-
Nürnberg (FAU), Germany. Among his awards and honors, he was elected a
lifetime honorary member of the Israel Chemical Society and a fellow of the
Royal Society of Chemistry (UK). Karsten received the Elhuyar-Goldschmidt Award from the Royal Society of
Chemistry of Spain, the Ludwig Mond Award from the RSC (UK), and the Chugaev Commemorative Medal
fromtheRussianAcademyofSciences.Hehasalsoenjoyedvisitingprofessorshippositionsattheuniversitiesof
Manchester(UK)andToulouse(F)aswellastheNagoyaInstituteofTechnology(JP)andETHZürich(CH).
TheMeyerlabresearchfocusesonthesynthesisofcustom-tailoredligandenvironmentsandtheirtransition
andactinidemetalcoordinationcomplexes.Thesecomplexesoftenexhibitunprecedentedcoordinationmodes,
unusual electronic structures, and, consequently, enhanced reactivities toward small molecules of biological
and industrial importance. Interestingly, Karsten’s favorite molecule is one that exhibits little reactivity: the
T symmetricU(dbabh) .
h 6
DermotO’HarewasborninNewry,CoDown.HestudiedatBalliolCollege,
Oxford University, where he obtainedhisB.A., M.A.,and D.Phil. degreesunder
the direction of Professor M.L.H. Green. In 1985, he was awarded a Royal
Commission of 1851 Research Fellowship, during this Fellowship he was a
visiting research fellow at the DuPont Central Research Department, Wilming-
ton, Delaware in 1986–87 in the group led by Prof. J.S. Miller working on
molecular-based magnetic materials. In 1987 he returned to Oxford to a
short-termuniversitylectureshipandin1990hewasappointedtoapermanent
university position and a Septcentenary Tutorial Fellowship at Balliol College.
HehaspreviouslybeenhonoredbytheInstitütdeFrance,AcadémiedesSciences
as a leading scientist in Europe under 40 years. He is currently professor of
organometallic and materials chemistry in the Department of Chemistry at the
UniversityofOxford.Inaddition,heiscurrentlythedirectoroftheSCG-Oxford
Centreof Excellencefor chemistry andassociatehead for business &innovation in the Mathematics, Physical
andLifeSciencesDivision.Heleadsamultidisciplinaryresearchteamthatworksacrossbroadareasofcatalysis
andnanomaterials.His research isspecificallytargetedatfinding solutionstoglobalissuesrelating toenergy,
zerocarbon,andthecirculareconomy.Hehasbeenawardednumerousawardsandprizesforhiscreativeand
vii
viii EditorBiographies
ground-breaking work in inorganic chemistry, including the Royal Society Chemistry’s Sir Edward Frankland
Fellowship,LudwigMondPrize,TildenMedal,andAcademia–IndustryPrizeandtheExxonEuropeanChem-
icalandEngineeringPrize.
Gerard Parkin received his B.A., M.A., and D.Phil. degrees from the Queen’s
College,OxfordUniversity,wherehecarriedoutresearchundertheguidanceof
Professor Malcolm L.H. Green. In 1985, he moved to the California Institute of
Technology as a NATO postdoctoral fellow to work with Professor John
E. Bercaw. He joined the Faculty of Columbia University as assistant professor
in 1988 and was promoted to associate professor in 1991 and to professor in
1994.HeservedaschairmanoftheDepartmentfrom1999to2002.Hehasalso
servedaschairoftheNewYorkSectionoftheAmericanChemicalSociety,chair
oftheInorganic ChemistryandCatalyticScienceSectionoftheNewYorkAcad-
emyofSciences,chairoftheOrganometallicSubdivisionoftheAmericanChem-
ical Society Division of Inorganic Chemistry, and chair of the Gordon Research
ConferenceinOrganometallicChemistry.
HeisanelectedfellowoftheAmericanChemicalSociety,theRoyalSocietyof
Chemistry, and the American Association for the Advancement of Science, and is the recipient of a variety of
internationalawards,includingtheACSAwardinpurechemistry,theACSAwardinorganometallicchemistry,
theRSCCordayMorganMedal,theRSCAwardinorganometallicchemistry,theRSCLudwigMondAward,and
the RSC Chem Soc Rev Lecture Award. He is also the recipient of the United States Presidential Award for
Excellence in Science, Mathematics and Engineering Mentoring,the United States Presidential FacultyFellow-
ship Award, the James Flack Norris Award for Outstanding Achievement in the Teaching of Chemistry, the
Columbia University Presidential Award for Outstanding Teaching, and the Lenfest Distinguished Columbia
FacultyAward.
Hisprincipalresearchinterestsareintheareasofsynthetic,structural,andmechanisticinorganicchemistry.
Volume Editors
Simon Aldridge is professor of chemistry at the University of Oxford and
director of the UKRI Centre for Doctoral Training in inorganic chemistry for
Future Manufacturing. Originally from Shrewsbury, England, he received both
hisB.A.andD.Phil.degreesfromtheUniversityofOxford,thelatterin1996for
work on hydride chemistry under the supervision of Tony Downs. After
post-doctoral work as a Fulbright Scholar at Notre Dame with Tom Fehlner,
and at Imperial College London (with Mike Mingos), he took up his first aca-
demic position at Cardiff University in 1998. He returned to Oxford in 2007,
beingpromotedtofullprofessorin2010.Prof.Aldridgehaspublishedmorethan
230 papers to date and is a past winner of the Dalton Transactions European
Lectureship (2009), the Royal Society of Chemistry’s Main Group Chemistry
(2010)andFranklandAwards(2018),andtheForschungspreisoftheAlexander
vonHumboldtFoundation(2021).Prof.Aldridge’sresearchinterestsareprimar-
ily focused on main group organometallic chemistry, and in particular the development of compounds with
unusualelectronicstructure,andtheirapplicationsinsmallmoleculeactivationandcatalysis(website:http://
aldridge.web.ox.ac.uk).
(Picturecredit:JohnCairns)
EditorBiographies ix
EszterBorosisassociateprofessorofchemistryatStonyBrookUniversitywith
courtesyappointmentsinradiologyandpharmacologyatStonyBrookMedicine.
EszterobtainedherM.Sc.(2007)attheUniversityofZurich,Switzerlandandher
Ph.D.(2011)inchemistryfromtheUniversityofBritishColumbia,Canada.She
was apostdoc (2011–15)and later instructor (2015–17) inradiology at Massa-
chusetts General Hospital and Harvard Medical School. In 2017, Eszter was
appointed as assistant professor of chemistry at Stony Brook University, where
her research group develops new approaches to metal-based diagnostics and
therapeutics at the interfaces of radiochemistry, inorganic chemistry and medi-
cine.Herlab’sworkhasbeenextensivelyrecognized;Eszterholdsvariousmajor
federal grants (NSF CAREER Award, NIH NIBIB R21 Trailblazer, NIH NIGMS
R35 MIRA) and has been named a 2020 Moore Inventor Fellow, the 2020
Jonathan L. Sessler Fellow (American Chemical Society, Inorganic Division),
recipient of a 2021 ACS Infectious Diseases/ACS Division of Biological Chemistry Young Investigator Award
(AmericanChemicalSociety),andwasalsonameda2022AlfredP.SloanResearchFellowinchemistry.
ScottR.DalyisassociateprofessorofchemistryattheUniversityofIowain
the United States. After spending 3 years in the U.S. Army, he obtained his B.S.
degree in chemistry in 2006 from North Central College, a small liberal arts
college in Naperville, Illinois. He then went on to receive his Ph.D. at the
University of Illinois at Urbana-Champaign in 2010 under the guidance of
Professor Gregory S. Girolami. His thesis research focused on the synthesis and
characterizationofchelatingborohydrideligandsandtheiruseinthepreparation
ofvolatilemetalcomplexesforchemicalvapordepositionapplications.In2010,
he began working as a Seaborg postdoctoral fellow with Drs. Stosh A. Kozimor
and David L. Clark at Los Alamos National Laboratory in Los Alamos, New
Mexico. His research there concentrated on the development of ligand K-edge
X-rayabsorptionspectroscopy(XAS)toinvestigatecovalentmetal–ligandbond-
ing and electronic structure variations in actinide, lanthanide, and transition
metal complexes with metal extractants. He started his independent career in 2012 at George Washington
UniversityinWashington,DC,andmovedtotheUniversityofIowashortlythereafterin2014.
Hiscurrentresearchinterestsfocusonsyntheticcoordinationchemistryandliganddesignwithemphasison
the development of chemical and redox noninnocent ligands, mechanochemical synthesis and separation
methods,andligandK-edgeXAS.HisresearchandoutreacheffortshavebeenrecognizedwithanOutstanding
Faculty/Staff Advocate Award from the University of Iowa Veterans Association (2016), a National Science
FoundationCAREERAward(2017),andaHawkeyeDistinguishedVeteransAward(2018).Hewaspromotedto
associateprofessorwithdistinctionasaCollegeofLiberalArtsandSciencesDeansScholarin2020.
Lena J. Daumann is currently professor of bioinorganic and coordination
chemistryattheLudwigMaximilianUniversitätinMunich.Shestudiedchemistry
attheUniversityofHeidelbergworkingwithProf.PeterCombaandsubsequently
conducted her Ph.D. at the University of Queensland (Australia) from 2010 to
2013holdingIPRSandUQCentennialfellowships.In2013shewaspartofthe
AustralianDelegationforthe63rdLindauNobelLaureatemeetinginchemistry.
FollowingpostdoctoralstaysatUCBerkeleywithProf.KenRaymond(2013–15)
and in Heidelberg, funded by the Alexander von Humboldt Foundation, she
started her independent career at the LMU Munich in 2016. Her bioinorganic
researchgroupworksonelucidatingtheroleoflanthanidesforbacteriaaswellas
onironenzymesandsmallbiomimeticcomplexesthatplayaroleinepigenetics
and DNA repair. Daumann’s teaching and research have been recognized with
numerousawardsandgrants.AmongthemarethenationalArsLegendiPrizefor
chemistry and the Therese von Bayern Prize in 2019 and the Dozentenpreis of the “Fonds der Chemischen
Industrie“ in 2021. In 2018 she was selected as fellow for the Klaus Tschira Boost Fund by the German Scholars
Organisationandin2020shereceivedaStartinggrantoftheEuropeanResearchCounciltostudytheuptakeof
lanthanidesbybacteria.
x EditorBiographies
DerekP.GateshailsfromHalifax,NovaScotia(Canada)wherehecompleted
his B.Sc. (Honours Chemistry) degree at Dalhousie University in 1993.
He completed his Ph.D. degree under the supervision of Professor Ian Manners
at the University of Toronto in 1997. He then joined the group of Professor
Maurice Brookhart as an NSERC postdoctoral fellow at the University of North
CarolinaatChapelHill(USA).Hebeganhisindependentresearchcareerin1999
as an assistant professor at the University of British Columbia in Vancouver
(Canada). He has been promoted through the ranks and has held the position
ofprofessorofchemistrysince2011.AtUBC,hehasreceivedtheScienceUnder-
graduate Society—Teaching Excellence Award, the Canadian National Commit-
tee for IUPAC Award, and the Chemical Society of Canada—Strem Chemicals
Award for pure or applied inorganic chemistry. His research interests bridge the
traditional fields of inorganic and polymer chemistry with particular focus on
phosphorus chemistry. Key topics include the discovery of novel structures, unusual bonding, new reactivity,
alongwithapplicationsincatalysisandmaterialsscience.
PatrickHollandperformedhisPh.D.researchinorganometallicchemistryatUC
Berkeley with Richard Andersen and Robert Bergman. He then learned about
bioinorganic chemistry through postdoctoral research on copper-O and
2
copper-thiolatechemistrywithWilliamTolmanattheUniversityofMinnesota.
His independent research at the University of Rochester initially focused on
systematic development of the properties and reactions of three-coordinate
complexes of iron and cobalt, which can engage in a range of bond activation
reactionsandorganometallictransformations.Sincethen,hisresearchgrouphas
broadened its studies to iron-N chemistry, reactive metal–ligand multiple
2
bonds, iron–sulfur clusters, engineered metalloproteins, redox-active ligands,
and solar fuel production. In 2013, Prof. Holland moved to Yale University,
whereheisnowConkeyP.WhiteheadProfessorofChemistry.Hisresearchhas
beenrecognizedwithanNSFCAREERAward,aSloanResearchAward,Fulbright
andHumboldtFellowships,aBlavatnikAwardforYoungScientists,andwaselectedasfellowoftheAmerican
Association for the Advancement of Science. In the area of N reduction, hisgroup has established molecular
2
principles to weaken and break the strong N–N bond, in order to use this abundant resource for energy and
synthesis.Hisgrouphasmadeaparticularefforttogainaninsightintoironchemistryrelevanttonitrogenase,
the enzyme that reduces N in nature. His group also maintains an active program in the use of inexpensive
2
metals for transformations of alkenes. Mechanistic details are a central motivation to Prof. Holland and the
wonderfulgroupofover80studentswithwhomhehasworked.
SteveLiddlewasborninSunderlandintheNorthEastofEnglandandgained
hisB.Sc.(Hons)andPh.D.fromNewcastleUniversity.Afterpostdoctoralfellow-
ships at Edinburgh, Newcastle, and Nottingham Universities he began his inde-
pendentcareeratNottinghamUniversityin2007withaRoyalSocietyUniversity
Research Fellowship. This was held in conjunction with a proleptic Lectureship
andhewaspromotedthroughtherankstoassociateprofessorandreaderin2010
andprofessorofinorganicchemistryin2013.HeremainedatNottinghamuntil
2015 when he was appointed professor and head of inorganic chemistry and
co-director ofthe CentreforRadiochemistry Researchat TheUniversityofMan-
chester.HehasbeenarecipientofanEPSRCEstablishedCareerFellowshipand
ERCStarterandConsolidatorgrants.HeisanelectedfellowofTheRoyalSociety
of Edinburgh and fellow of the Royal Society of Chemistry and he is vice
president to the Executive Committee of the European Rare Earth and Actinide
Society. His principal research interests are focused on f-element chemistry, involving exploratory synthetic
chemistrycoupledtodetailedelectronicstructureandreactivitystudiestoelucidatestructure-bonding-property
relationships. He is the recipient of a variety of prizes, including the IChemE Petronas Team Award for
Excellence in Education and Training, the RSC Sir Edward Frankland Fellowship, the RSC Radiochemistry
EditorBiographies xi
Group Bill Newton Award, a 41st ICCC Rising Star Award, the RSC Corday-Morgan Prize, an Alexander von
Humboldt Foundation Friedrich Wilhelm Bessel Research Award, the RSC Tilden Prize, and an RSC Dalton
DivisionHorizonTeamPrize.Hehaspublishedover220researcharticles,reviews,andbookchapterstodate.
DavidLiptrotreceivedhisMChem(Hons)inchemistrywithIndustrialTrain-
ingfromtheUniversityofBathin2011andremainedtheretoundertakeaPh.D.
ongroup2catalysisinthelaboratoryofProfessorMikeHill.Aftercompletingthis
in2015hetookupaLindemannPostdoctoralFellowshipwithProfessorPhilip
PowerFRS(UniversityofCalifornia,Davis,USA).In2017hebeganhisindepen-
dentcareerreturningtotheUniversityofBathandin2019wasawardedaRoyal
Society University Research Fellowship. His interests concern new synthetic
methodologies to introduce main group elements into functional molecules
andmaterials.
David P. Mills hails from Llanbradach and Caerphilly in the South Wales
Valleys.HecompletedhisMChem(2004)andPh.D.(2008)degreesatCardiff
University, with his doctorate in low oxidation state gallium chemistry super-
visedbyProfessorCameronJones.HemovedtotheUniversityofNottingham
in 2008 to work with Professor Stephen Liddle for postdoctoral studies in
lanthanide and actinide methanediide chemistry. In 2012 he moved to the
UniversityofManchestertostarthisindependentcareerasalecturer,wherehe
hassincebeenpromotedtofullprofessorofinorganicchemistryin2021.
Althoughheisinterestedinallaspectsofnonaqueoussyntheticchemistryhis
researchinterestsarecurrentlyfocusedonthesynthesisandcharacterizationof
f-blockcomplexeswithunusualgeometriesandbondingregimes,withtheaim
of enhancing physicochemical properties. He has been recognized for his con-
tributions to both research and teaching with prizes and awards, including a
Harrison-MeldolaMemorialPrize(2018),theRadiochemistryGroupBillNewtonAward(2019),andaTeam
Member of the Molecular Magnetism Group for the Dalton Division Horizon Prize (2021) from the Royal
Society of Chemistry. He was a Blavatnik Awards for Young Scientists in the United Kingdom Finalist in
Chemistryin2021andhecurrentlyholdsaEuropeanResearchCouncilConsolidatorGrant.
Ian Tonks is the Lloyd H. Reyerson professor at the University of Minneso-
taTwin Cities, and associate editor for the ACS journal Organometallics.
He received his B.A. in chemistry from Columbia University in 2006 and per-
formed undergraduate research with Prof. Ged Parkin. He earned his Ph.D. in
2012 from the California Institute of Technology, where he worked with Prof.
JohnBercawonolefinpolymerizationcatalysisandearlytransitionmetal-ligand
multiplybonded complexes.AfterpostdoctoralresearchwithProf. ClarkLandis
attheUniversityofWisconsin,Madison,hebeganhisindependentcareeratthe
UniversityofMinnesotain2013andearnedtenurein2019.Hiscurrentresearch
interestsarefocusedonthedevelopmentofearthabundant,sustainablecatalytic
methods using early transition metals, and also on catalytic strategies for incor-
poration of CO into polymers. Prof. Tonks’ work has recently been recognized
2
with an Outstanding New Investigator Award from the National Institutes of
Health, an Alfred P. Sloan Fellowship, a Department of Energy CAREER award, and the ACS Organometallics
Distinguished Author Award, among others. Additionally, Prof. Tonks’ service toward improving academic
safety culture was recently recognized with the 2021 ACS Division of Chemical Health and Safety Graduate
FacultySafetyAward.
