logam transisi & seny. koordinasi
TRANSCRIPT
![Page 1: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/1.jpg)
Transition Metals and Coordination Chemistry
Chapter 23Chapter 23
![Page 2: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/2.jpg)
Transition Metals
Similarities 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).
![Page 3: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/3.jpg)
![Page 4: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/4.jpg)
20_431
Ce
Th
Pr
Pa
Nd
U
Pm Sm
Pu
Eu
Am
Gd
Cm
Tb
Bk
Dy
Cf
Ho
Es
Er
Fm
Tm
Md
Yb
No
Lu
Lr
Sc
Y
La
Ac
Ti
Zr
Hf
Unq
V
Nb
Ta
Unp
Cr
Mo
W
Unh
Mn
Tc
Re
Uns
Fe
Ru
Os
Co
Rh
Ir
Ni
Pd
Pt
Cu
Ag
Au
Zn
Cd
Hg
Uno Une Uun Uuu
Np
![Page 5: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/5.jpg)
20_432
Sc
Y
La*
Ac†
Ti
Zr
Hf
Unq
V
Nb
Ta
Unp
Cr
Mo
W
Unh
Mn
Tc
Re
Fe
Ru
Os
Co
Rh
Ir
Ni
Pd
Pt
Cu
Ag
Au
Zn
Cd
Hg
Ce
Th
Pr
Pa
Nd
U
Pm
Np
Sm
Pu
Eu
Am
Gd
Cm
Tb
Bk
Dy
Cf
Ho
Es
Er
Fm
Tm
Md
Yb
No
Lu
Lr
d-block transition elements
*Lanthanides
† Actinides
f-block transition elements
Uns Uno Une Uun Uuu
![Page 6: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/6.jpg)
![Page 7: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/7.jpg)
![Page 8: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/8.jpg)
![Page 9: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/9.jpg)
![Page 10: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/10.jpg)
20_435
0.2
Ato
mic
radi
i (nm
)
Atomic number
La
Hf
TaW Re Os
Ir Pt
AuZr
Y
NbMo Tc Ru
Rh Pd
AgSc
Ti
VCr
Mn Fe Co Ni Cu
1st series (3d)
2nd series (4d)
3rd series (5d)
0.1
0.15
![Page 11: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/11.jpg)
Multiple Oxidation States
![Page 12: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/12.jpg)
Metallic Behavior/Reducing StrengthLower oxidation state = more metallicLower oxidation state = more metallic
![Page 13: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/13.jpg)
Color and Magnetism
e- in partially filled d sublevel absorbs visible light moves to slightly higher energy d orbital
Magnetic properties due to unpaired electrons
![Page 14: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/14.jpg)
Electronegativity increases down column
![Page 15: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/15.jpg)
ChromiumChemical properties reflect oxidation state
![Page 16: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/16.jpg)
Valence-State Electronegativity
Electronegativity, ENElectronegativity, EN::electron “pulling power”electron “pulling power”
Valence-state ENValence-state EN::metal in higher oxidation statemetal in higher oxidation state
is more positiveis more positivehas stronger pull on electronshas stronger pull on electronsis more electronegativeis more electronegative
““Effective ENEffective EN””
![Page 17: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/17.jpg)
Manganese
![Page 18: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/18.jpg)
Silver
![Page 19: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/19.jpg)
Weak Reducing Agent, H2Q
![Page 20: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/20.jpg)
Mercury
![Page 21: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/21.jpg)
Coordination Compound
Consist of a Consist of a complex ion complex ion and necessary and necessary counter ionscounter ions[Co(NH[Co(NH33))55Cl]ClCl]Cl22
Complex 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--
![Page 22: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/22.jpg)
Complex ion remains intact upon dissolution in water
[Co(NH3)6]Cl3 [Pt(NH3)4]Br2
![Page 23: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/23.jpg)
Complex Ion
Species 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 bases
Co(NHCo(NH33))663+3+
Pt(NHPt(NH33))33BrBr++
![Page 24: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/24.jpg)
![Page 25: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/25.jpg)
Ligands
Molecule 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 bond
monodentatemonodentate: 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 metal
ion possibleion possible
![Page 26: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/26.jpg)
![Page 27: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/27.jpg)
![Page 28: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/28.jpg)
Formulas of Coordination Compounds
1.1. Cation then anionCation then anion2.2. Total charges must balance to zeroTotal charges must balance to zero3.3. Complex ion in bracketsComplex ion in brackets
KK22[Co(NH[Co(NH33))22ClCl44]]
[Co(NH[Co(NH33))44ClCl22]Cl]Cl
![Page 29: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/29.jpg)
Names of Coordination Compounds
1.1. 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 -o
prefix indicates number of eachprefix indicates number of each
3.3. Oxidation stateOxidation state of metal ion in () only if more of metal ion in () only if more than one possiblethan one possible
4.4. If complex ion = anion, metal ending If complex ion = anion, metal ending -ate -ate
![Page 30: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/30.jpg)
![Page 31: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/31.jpg)
![Page 32: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/32.jpg)
Examples
KK22[Co(NH[Co(NH33))22ClCl44]]
potassium diamminetetrachlorocobaltate(II)potassium diamminetetrachlorocobaltate(II)
[Co(NH[Co(NH33))44ClCl22]Cl]Cl
tetraamminedichlorocobalt(III) chloridetetraamminedichlorocobalt(III) chloride
![Page 33: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/33.jpg)
![Page 34: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/34.jpg)
![Page 35: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/35.jpg)
20_441
Isomers(same formula but different properties)
Stereoisomers(same bonds, differentspatial arrangements)
Structuralisomers
(different bonds)
Opticalisomerism
Geometric(cis-trans)isomerism
Linkageisomerism
Coordinationisomerism
![Page 36: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/36.jpg)
Structural Isomerism 1
Coordination 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]SO44
![Page 37: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/37.jpg)
Structural Isomerism 2
Ligand 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]Cl
andand [Co(NH[Co(NH33))44(ONO)Cl]Cl(ONO)Cl]Cl
![Page 38: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/38.jpg)
Linkage 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)
chloridechloride
![Page 39: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/39.jpg)
Stereoisomerism 1
Geometric 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 ion
Pt(NHPt(NH33))22ClCl22
![Page 40: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/40.jpg)
![Page 41: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/41.jpg)
20_444
H3N
Co
H3N
NH3
NH3
Cl
Cl
H3N
Co
H3N
NH3
Cl
Cl
NH3
Cl
Cl
Co
Cl
ClCo
(a) (b)
![Page 42: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/42.jpg)
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_446
Unpolarizedlight
Polarizingfilter
Polarizedlight
Tubecontainingsample
Rotatedpolarized light
![Page 43: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/43.jpg)
20_448
Left hand Right hand
Mirror imageof right hand
![Page 44: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/44.jpg)
![Page 45: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/45.jpg)
20_449
N
N
N
N
N
NCo
N
N
N
N
N
NCo
Mirror imageof Isomer I
Isomer I Isomer II
N
N
N
N
N
NCo
![Page 46: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/46.jpg)
20_450
Cl
Cl
N
N
N
NCo
Cl
Cl
N
N
N
NCo
Cl
Cl
N
N
N
NCo
Cl
Cl
N
N
N
NCo
Cl
Cl
N
N
N
NCo
Isomer IIIsomer I
cistrans
Isomer II cannot besuperimposed exactlyon isomer I. They arenot identical structures.
The trans isomer andits mirror image areidentical. They are notisomers of each other.
Isomer II has the samestructure as the mirrorimage of isomer I.(b)(a)
![Page 47: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/47.jpg)
![Page 48: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/48.jpg)
![Page 49: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/49.jpg)
![Page 50: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/50.jpg)
Crystal Field Theory
Focus:Focus: energies of the energies of the dd orbitals orbitals
AssumptionsAssumptions
1.1. Ligands:Ligands: negative point negative point chargescharges
2.2. Metal-ligand bonding:Metal-ligand bonding: entirely ionicentirely ionic
strong-fieldstrong-field (low-spin): large splitting of (low-spin): large splitting of dd orbitals orbitalsweak-fieldweak-field (high-spin): small splitting of (high-spin): small splitting of dd orbitals orbitals
![Page 51: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/51.jpg)
![Page 52: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/52.jpg)
![Page 53: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/53.jpg)
20_454
eg(dz2, dx2 – y2)
t2g(dxz, dyz, dxy)
Free metal ion3d orbitalenergies
E
= crystal field splitting
![Page 54: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/54.jpg)
High spin Low spin
![Page 55: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/55.jpg)
![Page 56: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/56.jpg)
![Page 57: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/57.jpg)
![Page 58: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/58.jpg)
[V(H2O)6]2+ [V(H2O)6]3+
[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+s
![Page 59: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/59.jpg)
![Page 60: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/60.jpg)
![Page 61: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/61.jpg)
![Page 62: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/62.jpg)
20_459
–
–
–
– ––– ––
–
dz2 dx2 – y2
dxy dyzdxz
(a) (b)
Tetrahedral Complexes
![Page 63: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/63.jpg)
![Page 64: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/64.jpg)
20_461
E
Free metal ion Complex
dz2
dxy
dxz dyz
dx2 - y2
M z
(b)
Free metal ion Complex
dx2 - y2
dxydz2
dxz dyz
M
(a)
x
y
E
Square Planar & Linear Complexes
Approach along x-and y-axes Approach along z-axis
![Page 65: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/65.jpg)
![Page 66: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/66.jpg)
![Page 67: Logam Transisi & Seny. Koordinasi](https://reader033.vdocuments.site/reader033/viewer/2022061513/577ccefc1a28ab9e788e9403/html5/thumbnails/67.jpg)
Hemoglobin & Oxyhemoglobin