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CABRILLO CHEM 1B - Transition Metals

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Transition Metals and Coordination ChemistryTransition MetalsSlide 3Slide 4Slide 5Slide 6Slide 7Slide 8Slide 9Slide 10Multiple Oxidation StatesMetallic Behavior/Reducing StrengthColor and MagnetismSlide 14ChromiumValence-State ElectronegativityManganeseSilverWeak Reducing Agent, H2QMercuryCoordination CompoundSlide 22Complex IonSlide 24LigandsSlide 26Slide 27Formulas of Coordination CompoundsNames of Coordination CompoundsSlide 30Slide 31ExamplesSlide 33Slide 34Slide 35Structural Isomerism 1Structural Isomerism 2Linkage IsomersStereoisomerism 1Slide 40Slide 41Stereoisomerism 2Slide 43Slide 44Slide 45Slide 46Slide 47Slide 48Slide 49Crystal Field TheorySlide 51Slide 52Slide 53Slide 54Slide 55Slide 56Slide 57Slide 58Slide 59Slide 60Slide 61Tetrahedral ComplexesSlide 63Slide 64Slide 65Slide 66Hemoglobin & OxyhemoglobinTransition Metals and Coordination ChemistryChapter 23Chapter 23Transition MetalsSimilarities Similarities within a given period within a given period and and within a given group. within a given group.Last electrons added are inner electrons (Last electrons added are inner electrons (dd’s, ’s, ff’s).’s).20_431CeThPrPaNdUPm SmPuEuAmGdCmTbBkDyCfHoEsErFmTmMdYbNoLuLrScYLaAcTiZrHfUnqVNbTaUnpCrMoWUnhMnTcReUnsFeRuOsCoRhIrNiPdPtCuAgAuZnCdHgUno Une Uun UuuNp20_432ScYLa*Ac†TiZrHfUnqVNbTaUnpCrMoWUnhMnTcReFeRuOsCoRhIrNiPdPtCuAgAuZnCdHgCeThPrPaNdUPmNpSmPuEuAmGdCmTbBkDyCfHoEsErFmTmMdYbNoLuLrd-block transition elements*Lanthanides†Actinidesf-block transition elementsUns Uno Une Uun Uuu20_4350.2Atomic radii (nm)Atomic numberLaHfTaWReOsIrPtAuZrYNbMoTcRuRhPdAgScTiVCrMnFeCoNiCu1st series (3d)2nd series (4d)3rd series (5d)0.10.15Multiple Oxidation StatesMetallic Behavior/Reducing StrengthLower oxidation state = more metallicLower oxidation state = more metallicColor and Magnetisme- in partially filled d sublevel absorbs visible light moves to slightly higher energy d orbitalMagnetic properties due to unpaired electronsElectronegativity increases down columnChromiumChemical properties reflect oxidation stateValence-State ElectronegativityElectronegativity, ENElectronegativity, EN::electron “pulling power”electron “pulling power”Valence-state ENValence-state EN::metal in higher oxidation statemetal in higher oxidation stateis more positiveis more positivehas stronger pull on electronshas stronger pull on electronsis more electronegativeis more electronegative““Effective ENEffective EN””ManganeseSilverWeak Reducing Agent, H2QMercuryCoordination CompoundConsist of a Consist of a complex ion complex ion and necessary and necessary counter ionscounter ions[Co(NH[Co(NH33))55Cl]ClCl]Cl22Complex ion:Complex ion:[Co(NH[Co(NH33))55Cl]Cl]2+2+CoCo3+3+ + 5 NH + 5 NH33 + Cl + Cl-- ==1(3+) + 5 (0) + 1(1-)1(3+) + 5 (0) + 1(1-) = 2+= 2+Counter ions:Counter ions:2 Cl2 Cl--Complex ion remains intact upon dissolution in water[Co(NH3)6]Cl3[Pt(NH3)4]Br2Complex IonSpecies where transition metal ion is surrounded Species where transition metal ion is surrounded by a certain number of ligands.by a certain number of ligands.Transition metal ion:Transition metal ion:Lewis acidLewis acidLigands:Ligands:Lewis basesLewis basesCo(NHCo(NH33))663+3+Pt(NHPt(NH33))33BrBr++LigandsMolecule or ion having a lone electron pair that Molecule or ion having a lone electron pair that can be used to form a bond to a metal ion can be used to form a bond to a metal ion ((Lewis baseLewis base).).coordinate covalent bondcoordinate covalent bond: metal-ligand bond: metal-ligand bondmonodentatemonodentate: one bond to metal ion: one bond to metal ionbidentatebidentate: : two bond to metal iontwo bond to metal ionpolydentatepolydentate: : more than two bonds to a metalmore than two bonds to a metalion possibleion possibleFormulas of Coordination Compounds1.1.Cation then anionCation then anion2.2.Total charges must balance to zeroTotal charges must balance to zero3.3.Complex ion in bracketsComplex ion in bracketsKK22[Co(NH[Co(NH33))22ClCl44]][Co(NH[Co(NH33))44ClCl22]Cl]ClNames of Coordination Compounds1.1.Cation then anionCation then anion2.2.LigandsLigands in alphabetical order before metal ionin alphabetical order before metal ionneutral:neutral:molecule name*molecule name*anionic:anionic:-ide -ide  -o -oprefix indicates number of eachprefix indicates number of each3.3.Oxidation stateOxidation state of metal ion in () only if more of metal ion in () only if more than one possiblethan one possible4.4.If complex ion = anion, metal ending If complex ion = anion, metal ending  -ate -ateExamplesKK22[Co(NH[Co(NH33))22ClCl44]]potassium diamminetetrachlorocobaltate(II)potassium diamminetetrachlorocobaltate(II)[Co(NH[Co(NH33))44ClCl22]Cl]Cltetraamminedichlorocobalt(III) chloridetetraamminedichlorocobalt(III) chloride20_441Isomers(same formula but different properties)Stereoisomers(same bonds, differentspatial arrangements)Structuralisomers(different bonds)OpticalisomerismGeometric(cis-trans)isomerismLinkageisomerismCoordinationisomerismStructural Isomerism 1Coordination isomerism: Coordination isomerism: Composition of the complex ion varies.Composition of the complex ion varies.[Cr(NH[Cr(NH33))55SOSO44]Br ]Br and and [Cr(NH[Cr(NH33))55Br]SOBr]SO44Structural Isomerism 2Ligand isomerism: Ligand isomerism: Same complex ion structure but point of Same complex ion structure but point of attachment of at least one of the ligands differs.attachment of at least one of the ligands differs.[Co(NH[Co(NH33))44(NO(NO22)Cl]Cl)Cl]Clandand[Co(NH[Co(NH33))44(ONO)Cl]Cl(ONO)Cl]ClLinkage Isomers[Co(NH[Co(NH33))55(NO(NO22)]Cl)]Cl22Pentaamminenitrocobalt(III)Pentaamminenitrocobalt(III)chloridechloride[Co(NH[Co(NH33))55(ONO)]Cl(ONO)]Cl22Pentaamminenitritocobalt(III)Pentaamminenitritocobalt(III)chloridechlorideStereoisomerism 1Geometric isomerism (cis-trans):Geometric isomerism (cis-trans): Atoms or groups arranged differently spatially Atoms or groups arranged differently spatially relative to metal ionrelative to metal ionPt(NHPt(NH33))22ClCl2220_444H3NCoH3NNH3NH3ClClH3NCoH3NNH3ClClNH3ClClCoClClCo(a) (b)Stereoisomerism 2Optical isomerismOptical isomerism: : Have opposite effects on plane-polarized lightHave opposite effects on plane-polarized light(no superimposable mirror images)(no superimposable mirror images)20_446UnpolarizedlightPolarizingfilterPolarizedlightTubecontainingsampleRotatedpolarized light20_448Left handRight handMirror imageof right


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