Metal Ion Controlled Reactivity PDF
Preview Metal Ion Controlled Reactivity
Advances in INORGANIC CHEMISTRY Volume 61 ADVISORY BOARD I. Bertini P. A. Lay Universita` degliStudidiFirenze UniversityofSydney Florence,Italy Sydney,Australia D. J. Darensbourg A. E. Merbach TexasA&MUniversity LaboratoiredeChimieet CollegeStation Bioinorganique,EPFL Texas,USA Lausanne,Switzerland J. H. Espenson J. Reedijk IowaStateUniversity LeidenUniversity Ames,Iowa,USA Leiden,TheNetherlands L. H. Gade P. J. Sadler Universita¨tHeidelberg UniversityofWarwick Germany Warwick,England H. B. Gray Y. Sasaki CaliforniaInstituteofTechnology HokkaidoUniversity Pasadena,California,USA Sapporo,Japan M. L. H. Green K. Wieghardt UniversityofOxford Max-PlanckInstitut Oxford,UnitedKingdom Mu¨lheim,Germany Advances in INORGANIC CHEMISTRY EDITED BY Rudi van Eldik and Colin D. Hubbard Departmentof Chemistryand Pharmacy University ofErlangen-Nu¨rnberg 91058Erlangen Germany VOLUME 61: Metal Ion Controlled Reactivity AMSTERDAM(cid:2)BOSTON(cid:2)HEIDELBERG(cid:2)LONDON(cid:2)NEWYORK(cid:2)OXFORD PARIS(cid:2)SANDIEGO(cid:2)SANFRANCISCO(cid:2)SINGAPORE(cid:2)SYDNEY(cid:2)TOKYO ACADEMIC ACADEMICPRESSISANIMPRINTOFELSEVIER PRESS AcademicPressisanimprintofElsevier 32JamestownRoad,LondonNW17BY,UK Radarweg29,POBox211,1000AEAmsterdam,TheNetherlands 30CorporateDrive,Suite400,Burlington,MA01803,USA 525BStreet,Suite1900,SanDiego,CA92101-4495,USA Firstedition2009 Copyrightr2009ElsevierInc.Allrightsreserved Nopartofthispublicationmaybereproduced,storedinaretrievalsystem ortransmittedinanyformorbyanymeanselectronic,mechanical,photocopying, recordingorotherwisewithoutthepriorwrittenpermissionofthepublisher PermissionsmaybesoughtdirectlyfromElsevier’sScience&TechnologyRights DepartmentinOxford,UK:phone(þ44)(0)1865843830;fax(þ44)(0)1865853333; email:permissions@elsevier.com.Alternativelyyoucansubmityourrequestonlineby visitingtheElsevierwebsiteathttp://www.elsevier.com/locate/permissions,andselecting ObtainingpermissiontouseElseviermaterial Notice Noresponsibilityisassumedbythepublisherforanyinjuryand/ordamagetopersons orpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuse oroperationofanymethods,products,instructionsorideascontainedinthematerial herein.Becauseofrapidadvancesinthemedicalsciences,inparticular, independentverificationofdiagnosesanddrugdosagesshouldbemade LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN:978-0-12-375033-4 ISSN:0898-8838 ForinformationonallAcademicPresspublications visitourwebsiteatelsevierdirect.com PrintedandboundinUSA 0910111213 10987654321 CONTENTS LIST OFCONTRIBUTORS . . . . . . . . . . . . . . . ix PREFACE . . . . . . . . . . . . . . . . . . . xi Controlling Platinum, Ruthenium, and Osmium Reactivity for Anticancer Drug Design PIETER C.A. BRUIJNINCX and PETER J. SADLER I. Introduction . . . . . . . . . . . . . . . . 1 II. PlatinumAnticancer Prodrugs: A Photoactivation Strategy. . . 4 III. Ruthenium–Arene AnticancerDrugs . . . . . . . . . 21 IV. Osmium(II)–Arenes: A CytotoxicFamily of the Heavier Congener 51 V. ConcludingRemarks. . . . . . . . . . . . . . 57 Acknowledgments . . . . . . . . . . . . . . 58 References . . . . . . . . . . . . . . . . . 58 Design and Function of Metal Complexes as Contrast Agents in MRI VOJTEˇCH KUBI´CˇEK and E´ VA TO´TH I. Introduction . . . . . . . . . . . . . . . . 63 II. Relaxivity of GdIII Complexes: Optimization of the Relaxivity . . 67 III. StabilityAspects . . . . . . . . . . . . . . . 92 IV. ParamagneticCEST Agents. . . . . . . . . . . . 98 V. ResponsiveImagingProbes . . . . . . . . . . . . 101 VI. MnII Complexes in the Contextof MRI . . . . . . . . 109 VII. Non-Classical GdIII-BasedMRIContrast Agents . . . . . 115 VIII. Conclusionsand Outlook . . . . . . . . . . . . 119 References . . . . . . . . . . . . . . . . . 119 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 I. Introduction . . . . . . . . . . . . . . . . 131 II. Small-MoleculeMetal-Based Probes andTheir BiomedicalImaging Capabilities . . . . . . . . . . . . . . . . 137 v vi CONTENTS III. Conclusions . . . . . . . . . . . . . . . . 171 Acknowledgments . . . . . . . . . . . . . . 172 References . . . . . . . . . . . . . . . . . 172 Iron Sequestration by Small Molecules: Thermodynamic and Kinetic Studies of Natural Siderophores and Synthetic Model Compounds ALVIN L. CRUMBLISS and JAMES M. HARRINGTON I. Chemistryof IronandSiderophores . . . . . . . . . 179 II. SiderophoreStructure . . . . . . . . . . . . . 182 III. Thermodynamicsof Iron–Siderophore Interactions . . . . . 186 IV. ChelationKinetics of Iron–Siderophore Systems . . . . . . 220 V. SiderophoreRecognition andCellular Uptake . . . . . . 231 VI. Applications andFuture Directions in SiderophoreResearch . . 235 List ofStructure Numbers,Figures, and Abbreviations . . . . 240 Acknowledgments . . . . . . . . . . . . . . 242 References . . . . . . . . . . . . . . . . . 242 Calcium in Biological Systems JOHN BURGESS and EMMA RAVEN I. Introduction . . . . . . . . . . . . . . . . 252 II. TheCa2þ Aqua-Cation . . . . . . . . . . . . . 268 III. Calcium-Binding Metalloproteins . . . . . . . . . . 289 IV. Ca2þin Ionophores,Channels, andPumps . . . . . . . 308 V. CarbohydratesandCarboxylates . . . . . . . . . . 316 VI. Phosphates,Phosphonates,Nucleosides, andNucleotides . . . 321 VII. StabilityConstants:An Overview . . . . . . . . . . 326 VIII. Calcium-ContainingRigid Materials . . . . . . . . . 326 Ligand Abbreviations . . . . . . . . . . . . . 338 Acknowledgments . . . . . . . . . . . . . . 339 References . . . . . . . . . . . . . . . . . 339 Appendix: TheTerm Ligand . . . . . . . . . . . 365 New Developments in Synthetic Nitrogen Fixation with Molybdenum and Tungsten Phosphine Complexes AMELI DREHER, GERALD STEPHAN and FELIX TUCZEK I. Introduction . . . . . . . . . . . . . . . . 367 II. Mechanism ofthe ChattCycle: Experimental Investigations . . 371 III. Mechanism ofthe ChattCycle: Theoretical Investigations . . . 382 IV. MolybdenumDinitrogen Complexes withPolydentate Phosphineand MixedP/NLigands . . . . . . . . . 386 CONTENTS vii V. Conclusions . . . . . . . . . . . . . . . . 401 Acknowledgments . . . . . . . . . . . . . . 402 References . . . . . . . . . . . . . . . . . 402 Chemistry of Metalated Container Molecules BERTHOLD KERSTING and ULRIKE LEHMANN I. Introduction . . . . . . . . . . . . . . . . 407 II. MetalatedContainer Molecules: HostSystems and Complex Types 409 III. MetalatedContainer Molecules ofBinucleating Polyaza-DithiophenolateMacrocycles . . . . . . . . . 430 IV. Conclusion . . . . . . . . . . . . . . . . 457 Acknowledgments . . . . . . . . . . . . . . 458 References . . . . . . . . . . . . . . . . . 458 Mechanistic Considerations on the Reactivity of Green FeIII-TAML Activators of Peroxides ALEXANDER D. RYABOV and TERRENCE J. COLLINS I. Introduction . . . . . . . . . . . . . . . . 472 II. Speciationof TetraamideIron(III) Macrocycles in Solutionand theSolid State . . . . . . . . . . . . . . . 473 III. Kineticsand Mechanisms of Demetalation ofFeIII-TAML Activators . . . . . . . . . . . . . . . . . 478 IV. Catalysis-RelevantOxidized FormsDerivedfrom FeIII-TAMLs . 487 V. Mechanism ofCatalysis byTetraamide Macrocyclic FeIII-TAML Activatorsof HydrogenPeroxide,Functional Catalase-Peroxidase Replicas . . . . . . . . . . . . . . . . . 494 VI. TheActivity-Stability Parameterization of Homogeneous Green Oxidation Catalysts . . . . . . . . . . . . . . 510 VII. ConcludingRemarks. . . . . . . . . . . . . . 516 Acknowledgment . . . . . . . . . . . . . . . 517 References . . . . . . . . . . . . . . . . . 517 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 I. Introduction . . . . . . . . . . . . . . . . 523 II. Solvationof Metal Ions . . . . . . . . . . . . . 526 III. SolventExchangeMechanism . . . . . . . . . . . 533 viii CONTENTS IV. Conclusion . . . . . . . . . . . . . . . . 564 Acknowledgments . . . . . . . . . . . . . . 564 References . . . . . . . . . . . . . . . . . 564 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 I. Introduction . . . . . . . . . . . . . . . . 573 II. Chemistryof Fe(CO) Photofragments . . . . . . . . 577 5 III. OtherSpin-Forbidden Reactions of TransitionMetal Compounds. 606 IV. Spin-Forbidden Reactions: GeneralTrends . . . . . . . 609 V. Conclusions . . . . . . . . . . . . . . . . 616 Acknowledgments . . . . . . . . . . . . . . 618 References . . . . . . . . . . . . . . . . . 618 INDEX . . . . . . . . . . . . . . . . . . . . 625 CONTENTSOF PREVIOUSVOLUMES. . . . . . . . . . . . . 649 LIST OF CONTRIBUTORS Maria Besora James M. Harrington SchoolofChemistryandCentrefor DepartmentofChemistry,Duke ComputationalChemistry,University University,Durham,NC,USA ofBristol,Bristol,UnitedKingdom Jeremy N. Harvey Pieter C.A. Bruijnincx SchoolofChemistryandCentrefor DepartmentofChemistry,University ComputationalChemistry,University ofWarwick,Coventry, ofBristol,Bristol,UnitedKingdom UnitedKingdom Catrin James John Burgess ChemistryDepartment,University DepartmentofChemistry,Universityof ofBath,ClavertonDown, Leicester,Leicester,UnitedKingdom UnitedKingdom Jose´-Luis Berthold Kersting Carreo´n-Macedo Institutfu¨rAnorganischeChemie, SchoolofChemistryandCentrefor Universita¨tLeipzig,Leipzig, ComputationalChemistry,University Germany ofBristol,Bristol,UnitedKingdom; DepartmentofChemistry,University Vojteˇch Kub´ıcˇek ofAlberta,Edmonton,AB,Canada CentredeBiophysiqueMole´culaire, A´lvaro Cimas CNRS,Orle´ansCedex2,France SchoolofChemistryandCentrefor Ulrike Lehmann ComputationalChemistry,University ofBristol,Bristol,UnitedKingdom Institutfu¨rAnorganischeChemie, Universita¨tLeipzig,Leipzig, Terrence J. Collins Germany DepartmentofChemistry,Institute Bonita Lin forGreenScience,CarnegieMellon University,Pittsburgh,PA,USA OxfordSiemensMolecularImaging Laboratory,ChemistryResearch Timothy Conry Laboratory,UniversityofOxford, Oxford,UnitedKingdom OxfordSiemensMolecularImaging Laboratory,ChemistryResearch Sofia I. Pascu Laboratory,UniversityofOxford, Oxford,UnitedKingdom ChemistryDepartment,Universityof Bath,ClavertonDown;Oxford Alvin L. Crumbliss SiemensMolecularImaging Laboratory,ChemistryResearch DepartmentofChemistry,Duke Laboratory,UniversityofOxford, University,Durham,NC,USA Oxford,UnitedKingdom Ameli Dreher Ewa Pasgreta Institutfu¨ranorganischeChemie InorganicChemistry,Departmentof derChristianAlbrechtsUniversita¨t ChemistryandPharmacy,University zuKiel,Max-Eyth-Strasse2,Kiel, ofErlangen-Nu¨rnberg,Erlangen, Germany Germany ix
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