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Kimia Koordinasi :
Cabang ilmu kimia yang mempelajari tentang senyawa
koordinasi
Senyawa koordinasi :
Senyawa yang tersusun atas satu atom pusat (biasanya
logam atau kelompok atom seperti VO2, TiO, dll) dan ligan
(sejumlah anion atau molekul netral yang mengelilingi atom
atau kelompok atom pusat tersebut)
Ditinjau dari asam-basa Lewis, atom pusat dlm senyawa
koordinasi berperan sebagai asam, sedangkan ligan
sebagai basa Lewis
Periodic Table
d block transition elements
f bl
blockk transition
i i elements
l
d-Block
d
Block Transition Elements
IIIB IVB
VIIIB
VB VIB VIIB
Cr Mn Fe
IIB
Sc
Ti
Zr
Nb Mo
Tc
Ru Rh Pd Ag Cd
La
Hf
Ta
Re
Os
Co
IB
Ir
Ni Cu Zn
Pt Au Hg
M t hhave partially
Most
ti ll occupied
i d d subshells
b h ll in
i
common oxidation states
Electronic Configurations
g
Element
Sc
Ti
V
Cr
Mn
Configuration
[Ar]3d14s2
[[Ar]3d
] 24s2
[Ar]3d34s2
[Ar]3d54s1
[Ar]3d54s2
[[Ar]] = 1s22s22pp63s23pp6
Electronic Configurations
g
Element
Fe
Co
Ni
C
Cu
Zn
Configuration
[Ar] 3d64s2
[Ar] 3d74s2
[Ar] 3d84s2
[Ar]3d104s1
[Ar]3d104s2
[[Ar]] = 1s22s22pp63s23pp6
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe2+
Fe 2e- Fe2+
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe2+
Fe 2e- Fe2+
[Ar]3d64s2
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe2+
Fe 2e- Fe2+
[Ar]3d64s2
[Ar]3d6
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe3+
Fe 3e- Fe3+
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe3+
Fe 3e- Fe3+
[Ar]3d64s2
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe3+
Fe 3e- Fe3+
[Ar]3d64s2
[Ar]3d5
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Co3+
Co 3e- Co3+
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Co3+
Co 3e- Co3+
[Ar]3d74s2
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Co3+
Co 3e- Co3+
[Ar]3d74s2
[Ar]3d6
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Mn4+
Mn 4e- Mn4+
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Mn4+
Mn 4e- Mn4+
[Ar]3d54s2
Electronic Configurations of
Transition Metal Ions
Electronic configuration of Mn4+
Mn 4e- Mn4+
[Ar]3d54s2
[Ar]3d3
Coordination Chemistry
y
Transition metals act as Lewis acids
Form complexes/complex ions
Fe3+(aq) + 6CN-(aq) Fe(CN)63-(aq)
Lewis acid
Lewis base
Complex ion
Lewis base
Complex ion
Lewis base
Complex ion
Lewis base
Complex ion
Comple with
Complex
ith a net charge = complex
comple ion
Complexes have distinct properties
Coordination compound
Compound that contains 1 or more complexes
Example
[Co(NH3)6]Cl3
[Cu(NH3)4][PtCl4]
[Pt(NH3)2Cl2]
Coordination sphere
Metal and ligands bound to it
Coordination number
number of donor atoms bonded to the central
metal atom or ion in the complex
Most common = 4, 6
Determined by ligands
Larger ligands and those that transfer substantial
negative charge to metal favor lower coordination
numbers
6( 1)
6(-1)
6(0)
2(-1)
monodentate = 1
chelating agents
bidentate = 2
tetradentate = 4
hexadentate = 6
polydentate = 2 or more donor atoms
Ligands
Monodentate
Examples:
H2O,
O CN-, NH3, NO2-, SCN-, OH-, X- (halides),
(halides) CO
CO,
O2-
Example
p Complexes
p
[Co(NH3)6]3+
[Fe(SCN)6]3-
Ligands
g
Bidentate
Examples
oxalate ion = C2O42 ethylenediamine
y
((en)) = NH2CH2CH2NH2
ortho-phenanthroline (o-phen)
Example
p Complexes
p
[Co(en)3]3+
[Cr(C2O4)3]3 [Fe(NH3)4(o-phen)]3+
Ligands
g
oxalate ion
ethylenediamine
O
C
2-
CH2 CH2
H2N
NH2
ortho-phenanthroline
*N
*
D
Donor
A
Atoms
CH
CH
CH
HC
HC
CH
CH
CH
Ligands
oxalate ion
ethylenediamine
H
Ligands
Ligands
Hexadentate
ethylenediaminetetraacetate (EDTA) =
(O2CCH2)2N(CH2)2N(CH2CO2)24 Example Complexes
[Fe(EDTA)]-1
[Co(EDTA)]-1
Ligands
EDTA
*O
CH2
*O
CH2 C
O*
CH2 C
O*
CH2 CH2 N
CH2
O
Donor Atoms
Ligands
EDTA
H
C
M
Ligands
EDTA
Geometryy
Linear
Geometryy
Linear
Example: [Ag(NH3)2]+
tetrahedral
(most common)
square planar
(characteristic of metal ions with 8 d e-s)
Geometry
tetrahedral
square planar
Example: [Ni(CN)4]2-
Geometry
Geometry
octahedral
Geometry
6
Examples: [Co(CN)6]3-, [Fe(en)3]3+
octahedral
Porphyrin, an important
chelating agent found in
nature
N
NH
NH
N
Metalloporphyrin
N
2+
N
Fe
N
Nomenclature of Coordination
C
Compounds:
d IUPAC R
Rules
l
The cation is named before the anion
When naming a complex:
Ligands
Li
d are named
d fi
firstt
alphabetical order
Name
bromide, Br-
bromo
chloride, Cl-
chloro
cyanide, CN-
cyano
hydroxide, OH-
hydroxo
oxide, O2-
oxo
fluoride, F-
fluoro
Name
carbonate, CO32-
carbonato
oxalate, C2O42-
oxalato
sulfate, SO42-
sulfato
thiocyanate, SCN-
thiocyanato
thiosulfate, S2O32-
thiosulfato
Sulfite, SO32-
sulfito
Exceptions
water, H2O = aqua
a
ammonia,
o a, NH3 = a
ammine
e
carbon monoxide, CO = carbonyl
Name if in Cationic
Complex
Name if in Anionic
Complex
Sc
Scandium
Scandate
Ti
titanium
titanate
vanadium
vanadate
Cr
chromium
chromate
Mn
manganese
manganate
Fe
iron
ferrate
Co
cobalt
cobaltate
Ni
nickel
i k l
nickelate
i k l t
Cu
Copper
cuprate
Zn
Zinc
zincate
Isomerism
Isomers
compounds that have the same composition
but a different arrangement of atoms
Major Types
structural isomers
stereoisomers
Structural Isomers
Structural Isomers
isomers that have different bonds
Structural Isomers
Coordination
Coordination-sphere
sphere isomers
differ in a ligand bonded to the metal in the
complex as opposed to being outside the
complex,
coordination-sphere
Coordination-Sphere
Coordination
Sphere Isomers
Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Coordination-Sphere
Coordination
Sphere Isomers
Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Consider
C
id iionization
i ti iin water
t
[Co(NH3)5Cl]Br [Co(NH3)5Cl]+ + Br[Co(NH3)5Br]Cl [Co(NH3)5Br]+ + Cl-
Coordination-Sphere
Coordination
Sphere Isomers
Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Consider
C
id precipitation
i it ti
[Co(NH3)5Cl]Br(aq) + AgNO3(aq) [Co(NH3)5Cl]NO3(aq) + AgBr(aq)
[Co(NH3)5Br]Cl(aq) + AgNO3(aq) [Co(NH3)5Br]NO3(aq) + AgCl(s)
Structural Isomers
Linkage isomers
differ in the atom of a ligand bonded to the
metal in the complex
Linkage Isomers
Example
[Co(NH3)5(ONO)]2+ vs. [Co(NH3)5(NO2)]2+
Linkage
g Isomers
Linkage Isomers
Example
[Co(NH3)5(SCN)]2+ vs. [Co(NH3)5(NCS)]2+
Co-SCN vs. Co-NCS
Stereoisomers
Stereoisomers
Isomers that have the same bonds, but
different spatial arrangements
Stereoisomers
Geometric isomers
Differ in the spatial arrangements of the
ligands
Geometric Isomers
cis isomer
trans isomer
Pt(NH3)2Cl2
Geometric Isomers
cis isomer
trans isomer
[Co(H2O)4Cl2]+
Stereoisomers
Geometric isomers
Differ in the spatial arrangements of the
ligands
Have different chemical/physical properties
different colors,
colors melting points
points, polarities
polarities,
solubilities, reactivities, etc.
Stereoisomers
Optical isomers
isomers that are nonsuperimposable mirror
images
said to be chiral (handed)
referred to as enantiomers
Example 1
mirroor plane
cis-[Co(en)2Cl2]+
Example 1
rotate mirror
i
image
i
180
180
Example 1
nonsuperimposable
cis-[Co(en)2Cl2]+
Example 1
enantiomers
cis-[Co(en)2Cl2]+
Example 2
mirrror plan
ne
trans [Co(en)2Cl2]+
trans-[Co(en)
Example 2
rotate mirror
i
image
i
180
180
trans [Co(en)2Cl2]+
trans-[Co(en)
Example 2
trans [Co(en)2Cl2]+
trans-[Co(en)
different in:
interactions with plane polarized light
Optical Isomers
polarizing
filter
light
source
plane
polarized
l i d light
li h
unpolarized
light
(random vibrations)
Optical Isomers
polarizing filter
plane
polarized
light
rotated polarized
light
Optical Isomers
polarizing filter
plane
polarized
light
rotated polarized
light
different in:
interactions with plane polarized light
reactivity
ti it with
ith chiral
hi l reagents
t
Example
d C4H4O62-(aq) + d,l
d-C
d,l-[Co(en)
[Co(en)3]Cl3(aq)
d-[Co(en)3](d-C4H4O62- )Cl(s) + l-[Co(en)3]Cl3(aq) +2Cl(aq)