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Coordination Chemistry

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

Sifatt senyawa kkoordinasi


Sif
di
id
dapatt di
diprediksi
dik i d
darii
Sifat ion pusatnya, dan
Sifat ligan
Ju a muatan
Jumlah
uata kompleks
o pe sd
ditentukan
te tu a da
dari pe
penjumlahan
ju a a
muatan ion pusat dan ligan yang membentuk kompleks.
Spesies kompleks dapat berupa non-ionik, kation dan
anion, bergantung pada muatan penyusunnya

Why Study Transition Metals and Their


C
Compounds
d
Manyy biomolecules contain transition metals that are
involved in the functions of these biomolecules
Vitamin B12 contains Co
Hemoglobin,
Hemoglobin myoglobin
myoglobin, and cytochrome C are iron
complexes
Chlorophyll is a magnesium complex
Transition metals and their compounds have many useful
applications
Transition metal compounds
p
are used as p
pigments
g
TiO2 = white
PbCrO4 = yellow
Fe4[Fe(CN)6]3 (prussian blue)= blue

Transition metal compounds are used in many industrial processes

To understand the uses and applications of


transition metals and their compounds, we need
to understand their chemistry.

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

valence ns e-s removed


first

Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe2+

Fe 2e- Fe2+
[Ar]3d64s2

[Ar]3d6

valence ns e-s removed


first

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

valence ns e-s removed


first, then n-1 d e-s

Electronic Configurations of
Transition Metal Ions
Electronic configuration of Fe3+

Fe 3e- Fe3+
[Ar]3d64s2

[Ar]3d5

valence ns e-s removed


first, then n-1 d e-s

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

valence ns e-s removed


first, then n-1 d e-s

Electronic Configurations of
Transition Metal Ions
Electronic configuration of Co3+

Co 3e- Co3+
[Ar]3d74s2

[Ar]3d6

valence ns e-s removed


first, then n-1 d e-s

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

valence ns e-s removed


first, then n-1 d e-s

Electronic Configurations of
Transition Metal Ions
Electronic configuration of Mn4+

Mn 4e- Mn4+
[Ar]3d54s2

[Ar]3d3

valence ns e-s removed


first, then n-1 d e-s

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

Ni2+(aq) + 6NH3(aq) Ni(NH3)62+(aq)


Lewis acid

Lewis base

Complex ion

Complex contains central metal ion bonded to one or more


molecules or anions
Lewis acid = metal = center of coordination
Lewis base = ligand = molecules/ions covalently bonded to
metal in complex

Transition metals act as Lewis acids


Form complexes/complex ions
Fe3+(aq) + 6CN-(aq) [Fe(CN)6]3-(aq)
Lewis acid

Lewis base

Complex ion

Ni2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq)


Lewis acid

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

Complex charge = sum of charges


on the
h metall andd the
h ligands
li d
[Fe(CN)6]3-

Complex charge = sum of charges


on the
h metall andd the
h ligands
li d
[Fe(CN)6]3+3

6( 1)
6(-1)

Neutral charge of coordination compound = sum of


charges
h
on metal,
l ligands,
li d andd counterbalancing
b l i ions
i
[Co(NH3)6]Cl2
neutral compound
p

Neutral charge of coordination compound = sum of


charges
h
on metal,
l ligands,
li d andd counterbalancing
b l i ions
i
[Co(NH3)6]Cl2
+2

6(0)

2(-1)

Classification of coordination compound


Ligands
classified according to the number of donor
atoms
Examples

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

Common Geometries of Complexes


Coordination Number

Geometryy

Linear

Common Geometries of Complexes


Coordination Number

Geometryy

Linear
Example: [Ag(NH3)2]+

Common Geometries of Complexes


Coordination Number

tetrahedral
(most common)

square planar
(characteristic of metal ions with 8 d e-s)

Geometry

Common Geometries of Complexes


Coordination Number

tetrahedral

Examples: [Zn(NH3)4]2+, [FeCl4]-

square planar
Example: [Ni(CN)4]2-

Geometry

Common Geometries of Complexes


Coordination Number

Geometry

octahedral

Common Geometries of Complexes


Coordination Number

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

Myoglobin, a protein that


stores O2 in cells

Coordination Environment of Fe2+ in


Oxymyoglobin
y y g
and Oxyhemoglobin
y
g

Ferrichrome (Involved in Fe transport in


bacteria)

Berdasarkan pada jenis ikatan koordinasi yang


terbentuk ligan dapat dikelompokkan sebagai :
terbentuk,
-Ligan yg tdk punya elektron yang sesuai untuk
ikatan dan orbital kosong shg ikatan yang
terbentuk hanya , seperti H-, NH3, SO32- atau
RNH2
-Ligan yang memiliki 2 atau 3 pasang elektron
nonbonding,seperti
g p
N3-, O2-, F-, Cl-, Br-, I-, OH-, S2-,
NH2-, H2O, R2S, R2O dan NH2
-Ligan yg memiliki orbital -anti ikatan kosong
dgn energi rendah dapat menerima elektron yg
orientasinya sesuai dari logam spt CO, R3P, R3As,
B I-,
Br-,
I CN-,
CN py dan
d acac

Ligan yg tidak ada pasangan elektron nonbonding nya tetapi


memiliki
iliki elektron
l kt
ik t
ikatan-,
seperti
ti alkena,
lk
alkina,
lki
b
benzena
d
dan
anion siklopentadienil
- Ligan yg dapat membentuk 2 ikatan dengan 2 atom logam
t i h dan
terpisah
d kemudian
k
di membentuk
b t k jembatan.
j b t
Mi l
Misalnya
OH-, Cl-, F-,
NH2-, O2-, CO, SO42- dan O2Jenis logam
Berdasarkan konfigurasinya:
- Ion dengan konfigurasi sama dengan konfigurasi gas mulia
ion ini dpt membentuk ikatan mulai dari bersifat ionik sampai kovalen sesuai dengan kenaikan
muatan ionnya

Ion dengan 18 elektron


ion dg konfigurasi ns2 np6 nd10 juga simetri scr spherical termasuk logam-logam transisi dan
keadaan oksida negatif

Ion pasangan inert (ns2)


Ion logam transisi (ndx, x = 1-9)

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

Metal atom/ion is named last


oxidation state given in Roman numerals follows in
parentheses

Use no spaces in complex name

Nomenclature: IUPAC Rules


The names of anionic ligands end with the
suffix -o
-ide
ide suffix changed to -o
o
-ite suffix changed to -ito
-ate
ate suffix changed to -ato
ato

Nomenclature: IUPAC Rules


Ligand

Name

bromide, Br-

bromo

chloride, Cl-

chloro

cyanide, CN-

cyano

hydroxide, OH-

hydroxo

oxide, O2-

oxo

fluoride, F-

fluoro

Nomenclature: IUPAC Rules


Ligand

Name

carbonate, CO32-

carbonato

oxalate, C2O42-

oxalato

sulfate, SO42-

sulfato

thiocyanate, SCN-

thiocyanato

thiosulfate, S2O32-

thiosulfato

Sulfite, SO32-

sulfito

Nomenclature: IUPAC Rules


Neutral ligands are referred to by the usual
name for the molecule
Example
ethylenediamine

Exceptions
water, H2O = aqua
a
ammonia,
o a, NH3 = a
ammine
e
carbon monoxide, CO = carbonyl

Nomenclature: IUPAC Rules


Greek prefixes are used to indicate the number
of each type
y of ligand
g
when more than one is
present in the complex
di-, 2; tri-, 3; tetra-, 4; penta-, 5; hexa-, 6

If the ligand name already contains a Greek


prefix, use alternate prefixes:
bis-, 2; tris-, 3; tetrakis-,4; pentakis-, 5; hexakis-, 6
The name of the ligand is placed in parentheses

Nomenclature: IUPAC Rules


If a complex is an anion
anion, its name ends
with the -ate
appended to name of the metal
Example
[Co(NO2)6]3- ; heksanitritokobaltat(III)

Nomenclature: IUPAC Rules


Transition
Metal

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

A substance is chiral if it does not have a


plane of symmetry

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

Superimposable not enantiomers


Superimposable-not

trans [Co(en)2Cl2]+
trans-[Co(en)

Properties of Optical Isomers


Enantiomers
possess many identical properties
solubility
solubility, melting point
point, boiling point
point, color
color,
chemical reactivity (with nonchiral reagents)

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)

(vibrates in one plane)

Optical Isomers
polarizing filter

plane
polarized
light

optically active sample


in solution

rotated polarized
light

Optical Isomers
polarizing filter

plane
polarized
light

optically active sample


in solution

Dextrorotatory (d) = right


rotation
Levorotatory (l) = left rotation
Racemic mixture = equal
amounts of two enantiomers; no
net rotation

rotated polarized
light

Properties of Optical Isomers


Enantiomers
p
possess many
y identical p
properties
p
solubility, melting point, boiling point, color, chemical
reactivity (with nonchiral reagents)

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)

Properties of transition metal complexes:


usually have color
dependent upon ligand(s) and metal ion

many are paramagnetic


due to unpaired
p
d electrons
degree of paramagnetism dependent on ligand(s)
[Fe(CN)6]3- has 1 unpaired d electron
3 h
[FeF
[F F6]3has 5 unpaired
i d d electrons
l t