Organometallic and Coordination Chemistry of the Actinides

197 Pages·2008·5.51 MB·English

by  Manab Sharma

127
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Organometallic and Coordination Chemistry
of the Actinides
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Withcontributionsby
S.C.Bart·F.G.N.Cloke·M.S.Eisen·K.Meyer
M.Sharma·O.T.Summerscales
123
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Preface
Thisvolumereviewsrecent developmentsinthefieldsoforganometallicand
coordinationchemistryoftheactinides,andinparticularuranium.Actinide
chemistryingeneralhasrecentlybeenrejuvenatedwithdemonstrationsofun-
precedentedstructures,reactivity,andphysicalproperties.Whileorganoura-
nium chemistry can be traced back to the Manhattan Project, most of these
efforts were unsuccessful. However, by the mid-1950s the first uranium cy-
clopentadienyl (Cp) complexes were being reported, e.g. tricyclopentadienyl
uranium(IV)chloride,(C H ) UCl.Thelate1960sheraldedthesynthesisand
5 5 3
structural elucidation of “uranocene,” bis(cyclooctatetraenyl)uranium(IV),
U(C H ) , an expanded-ring sandwich compound that provided tantalizing
8 8 2
evidence that 5f orbitals might be involved in bonding. One of the chapters
in this volume details the expansion of this kind of work to include mixed
sandwichU(III)cyclooctatetraeneandpentalenecomplexes.Asdiscussedby
several of the authors, the availability of easily prepared mid-valent start-
ing materials has been oneof the primary factors involved in reinvigorating
thisfield. Of particular interest to many readers willbe the binding ofsmall
moleculesbybothorganometallicandcoordinationcompoundsofuranium.
Someoftheholygrailsofthischemistryincludetheactivationofdinitrogen,
carbon monoxide, and carbon dioxide. Various aspects of this work can be
foundinallthreechapters,butaredetailedinparticularbyO.T.Summerscales
andF.G.N.Cloke.
The originsofcoordinationcompoundsofuranium aredifficulttodefine
preciselybecausethedefinitionofwhatconstitutesacoordinationcompound
versusapurelyinorganiccompoundcanbedifficulttodifferentiate.However,
thecoordinationchemistryofuraniumisveryold,datingbacktoatleastthe
early1800s.Thereistremendousdiversityinthetypeofligandsthathavebeen
found to form stable complexes with uranium. Recent work has focused on
highly tailored ligand sets toyield specific physico-chemicalresponses. This
work has included the development of uranium complexes that specifically
bindsmallmoleculessuchascarbondioxide.Inaddition,heterometallic3d-5f
systems are now being developed to explore magnetic interactions. It is im-
portantnottooverlookearlypioneeringeffortsbyT.J.Marksandco-workers,
whoamongotherkey discoveriesfoundthaturanylcationscantemplatethe
formationof superphthalocyanines. S.C. Bart and K. Meyer’s chapter details
X Preface
more recent advances in the coordination chemistry of uranium in mid- to
highoxidationstates.
Oneofthemostexcitingandactiveareasofactinideresearchinvolvesthe
developmentofnovelcatalysts.Thoriumanduraniummetallocenecomplexes
havebeenshowntoreactinhighlyspecificmannersthatinsomecasesparallel
thoseofearlytransitionmetals,andinothersthereactionsareuniquetothe
actinides.M.SharmaandM.S.Eisen’schapterdetailsmetalloceneorganoac-
tinidechemistrywithaspecialfocusonnovelreactionpathwaysthathavein
somecasesbeendeducedfromthermochemicalstudies.
Insummary,thepublicationofthisvolumeisastrongindicatorofthesub-
stantialactivitycurrentlytakingplaceintheorganometallicandcoordination
chemistriesoftheactinides.Thefuturepromisestoholdmanymoresurprises.
Auburn,December2007 ThomasE.Albrecht-Schmitt
Contents
MetalloceneOrganoactinideComplexes
M.Sharma·M.S.Eisen . . . . . . . . . . . . . . . . . . . . . . . . . . 1
ActivationofSmallMolecules
byU(III)CyclooctatetraeneandPentaleneComplexes
O.T.Summerscales·F.G.N.Cloke. . . . . . . . . . . . . . . . . . . . . 87
HighlightsinUraniumCoordinationChemistry
S.C.Bart·K.Meyer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
AuthorIndexVolumes101–130 . . . . . . . . . . . . . . . . . . . . . . 177
SubjectIndex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
StructBond(2008)127:1–85
DOI10.1007/430_2008_082
© Springer-VerlagBerlinHeidelberg
Publishedonline:10April2008
MetalloceneOrganoactinideComplexes
ManabSharma·MorisS.Eisen((cid:1))
SchulichFacultyofChemistry,InstituteofCatalysisScienceandTechnology,
Technion–IsraelInstituteofTechnology,TechnionCity,32000Haifa,Israel
[email protected]
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 SynthesisandReactivityofActinideComplexes . . . . . . . . . . . . . . . 4
2.1 TrivalentActinideCpComplexes. . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 StericallyInducedReduction . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 Displacementof(C5Me5)1– Ligands . . . . . . . . . . . . . . . . . . . . . . 14
2.4 BridgingComplexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5 AffinityTowardsLewisBases . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.6 MetalLigandBackDonation . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.7 BeyondtheTris-CpComplexes . . . . . . . . . . . . . . . . . . . . . . . . . 32
3 TetravalentChemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4 ConclusionandPerspectives . . . . . . . . . . . . . . . . . . . . . . . . . . 76
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Abstract Duringthelastdecade,thechemistryofd0/fnactinideshasflourishedreaching
a high levelof sophistication. Comparedtothe early or latetransition-metal complexes
andlanthanides,theactinidessometimesexhibit parallelbutmostlycomplementaryac-
tivitiesforsimilarorganicprocesses, andsometimesevenchallengetheactivitiesofthe
transitionmetals.ArapidincreaseinthenumbersofreportsintheCambridgedatabase
alsoreflectstheircurrent importance.Inviewoftheabove,inthisparticularreviewwe
have provided an overview and updated information about the preparation and prop-
erties of the major classes of actinide complexes containing different cyclopentadienyl
ligandsandhavingtheoxidationstates(+3and+4).
Keywords Metallocenecomplexes·Organoactinides·Stericallyinducedreduction(SIR)
Abbreviations
Cp Cyclopentadienyl,η5-C5H5
Cp(cid:1) η5-C(CH3)3C5H4
Cp(cid:2)= η5-(CH3)C5H4
Cpφ η5-{Si(CH3)3}C5H4
Cp(cid:1)(cid:1) η5-1,3-{Si(CH3)3}2C5H3
Cp# η5-1,3-{C(CH3)3}2C5H3
Cp∗ η5-(CH3)5C5
(cid:1)(cid:1)(cid:1)
Cp (CH3)4C5
COT η-C8H8