Coordination

Compounds
chemistry Kaarya Murugan 12507

Coordination Compound Compounds consisting of a central metal atom or ion bonded

to a fixed number of ions or molecules called ligands

WERNER'S THEORY

ination compounds metals show two types of linkages valences primary

froma Eliences are
normally ionisable and are satisfied by negative ions
iv secondary valences are non ionisable are satisfied by neutral molecules or
negative ions Secondary valence is equal to coordination number and is fixed for a

T.IE ions groups bound by the secondary linkages to the metal have characterist
spatial arrangements corresponding to different coordination numbers
nter ion
COCNM
Tordinatoncomplexentity

fifi.si anbeta
seatestitptIey Eto Imp Ett
t.no tasaiss iaie
E

IMPORTANT TERMS
F
al metal atom or ion bonded to fixed number of ions or
molecules

when foxed number of ions groups are bound in definite

geometrical arrangement around it Also referred to as Lewis acids
 Eni I
Fe CN

Ligands

In fate Then Ian is thund melt L through single donor

E g ce H2O NMs
Didentate when ligand can bind through two donor atoms
E.gethane 1,2 diamine c out
Polydentate when several donor atoms are present in single ligand
E.g EDTA cmaco
Mac n
cmcoo Etehy.li eqgmonetetraacetate
one
male
n enacoo
Lamacoo
chelate ligand when di or polydentate ligand uses its two or more donor
atoms simultaneously to bind a single metal ion
Number of such ligating groups is denticity of the ligand
chelate complexes are more stable than complexes w unidentate ligands

ambidentate atoms and either of the two

t.gg iiggsesatniggfgEentcomdpie

Esi S

n o
Titania n
m o
not
nitrito o

9975 notNY.orgnd donor atoms to which the metal is directly bonded

fit
Coordination sphere
Kaffeanthscoordination sphere Fe CN
Counter
ion K
Coordination Polyhedron
ftp.aatfalatgtgige.ment of the ligand atoms which are directly attached to the
L L
i
Emiri
L L mini L
m
2 iii Iris
octahedral Tetrahedral square planar pythoda pythmodal
0
95 fmbEud castrate the ligands are removed along with the
e'ftp.tsent drsbythatroitnshnEnederayitfnthepar.ttstsatfFier coordination entity
Cu Ccn Ca I

slept nd
Eg its only one kind of donor

e bound to more than one kind of donor group

I roleph Egg
NAMING COORDINATION COMPLEXES

IIE
ii Naming of ligands
1 Eggs List ligands alphabetically before metal
aic monsi co nitrossi no
an
iaim
c it
fi igaiaeant itex
p m

Ing the central metal atom

EE c s Ii na ntiie

Ii
emanate as
EE
Roman numerals in parentheses
Y ce 5 II ifeng.it teii
in writing the complete name
combine names of the ligands central metal oxidation state
Name complex ion first followed by counter son
v Points to keep in mind
spaces in the formula
I Sp a.net EaysrehosYaitteapnagiethoiaty
use parantheses for prefixes like bis tries
Ensure charge balance in overall formula
ISOMERISM IN COORDINATION COMPOUNDS
STEREOISOMERISM possible in tetrahedral unidentate
It
GEOMETRIC isomerism
Occurs due to different geometric arrangements of ligands in heteroleptic complexes
i
as Iy P's cent Ipposite trans
ce NHz
Pt PtCNMsaClz
Ce mm
cis trans
ii dra mxala
99 Gamplexes

it
ce
caruncest
cis trans
facial meridional

yep yep coins no s

ON nm ON Noz
mer fac
s
Ptolfts in Ea Momplexes that cannot be superimposed on their mirror images
called enantiomers
7 on
Do
V1 Egan
dextro laevo

SEE.IR dmer'SMERISM
arises when ambidentate ligands form different bonds
E.g redform when bound through oxygen cano
co Nhs no re yellow form when bound thru nitrogenC NO
mE
1
Name FEchange of ligands between cationic and anionic
parts a
F9
co so er 6 Coles c 376
 ftp.ga tttF e oragannmptegnene
itself a potential ligand and can

co NH _Be Sfa Co Nhs sea By

SOLVATE ISOMERISM aka hydrate isomerism
molecule is directly bonded to metal ion
Piffs's pf In Yystfrlafc.at
or 6 res violet a or s e ch greygreen

LIMITATIONS OF WERNER'S THEORY

Gert Ye'SentsToild form coordination compounds
bonds coordination compounds have directional properties
in
coordination compounds have characteristic magnetic and optical properties

VALENCE BOND THEORY

of S.ie Edneinceifar9namt iaf p nndsuna in fingen.tn fhygraidaigatoon

If 2 gge.my ds
aton of its orbitals s p d to form equivalen
Hybridized orbitals overlap with ligand orbitals donating lone pairs of electrons

ii magnetic Properties
Determined
by presence or absence of unpaired electrons
iii Geometry
Type of hybridisation dictatesgeometry

I IE i i
HYBRIDIZATIONS GEOMETRIES

ON GEOMETRY
COLETTE 1195 sation
Tetrahedral
1 squareplanar
sp'd trigonal bipyramidal
sp'd
disps
EYE
Find of co
991 sate

Draw orbitals for Cots

co Car us 3d
cots Car as 3ds
11 9
31 Is up
a sps hybridisedorbitals NH behaves as strong field ligand and causes
pairing of electrons in lower energyorbitals
It did
daspshybrid
CoCNH

111111 11117171171
six pairs of electrons from six Nu ligand molecules

sn
i i
ie
magnetic moment µ Fti n no of unpaired e

STRONG WEAK FIELD LIGANDS

of electrons in lower energy orbitals
9cnÉe 99yd en Pegging

weak field ligands Do not cause pairing

E.g I Br ce F on_ CNS NO

spectrochemical series
I Br ce c f con Hao NCS c edta NHycen CCN CO
WFL
H2O is a moderate ligand Its behaviour as strong or weak Stipends
on the metal ion

LIMITATIONS OF VALENCE BOND THEORY

i Involves number of assumptions
it Does not give quantitative interpretation of magnetic data
iii Does not explain colour exhibited by coordination compounds
iv Does not give quantitative interpretation of thermodynamic or kinetic stabilities
ftp.Furesotofmakeycostqfntatepreiiptg.rs regarding tetrahedral or square planar
vi Does not distinguish between weak strong ligands
CRYSTAL FIELD THEORY
Explains the interaction between the central metal ion and ligands in coordination
compounds assuming that the metal ligand bond is ionic

EE E si ie i i

EE i
m.me

CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COMPLEXES

1 What happens

I i a ans
si
These orbitals point directly toward the ligands so they experience maximum
repulsion and are raised in energy
Lower energy tag dry dxz dyz
These orbitals point between the ligands so they experience less repulsion
are lower in energy

2 Energy splitting
Energy difference between tag and eg orbitals is crystal field splitting Energy

t.gs 5 i ad i sYy
pairingenergy
SisTso
3 How electrons foll orbitals
For weak field ligands so P electrons prefer to remain unpaired
For strong field ligands so P electrons pair in lower tag orbitals

T.FI idp a 9Ccrg ret ipainede low spin

CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COMPLEXES
1 what happens
Four ligands surround the centralmetal ion

EEen.gg e da f'sanatoa teabInei experience Y repulsion

Higherenergy E day dyz and dy closer experience more repulsion
2 Energy splitting
Energy difference is Δt tetrahedral splitting energy
It is much smaller than do because there are fewer ligands and les
JPY ya so
I i s iii in
 3 How electrons fill orbitals
since It is small pairing energy is usually larger than St so high spin
configurations are common
COLOUR IN COORDINATION COMPOUNDS
colour arises from the absorption of visible light which promotes electrons from
tag to eg orbitals absorbed
wavelength of light depends on CFSE Do
smaller so longer wavelength absorbed
larger so shorter wavelength absorbed
observed colour is complementary to absorbed colour
In absence of ligands without a crystal field no splitting occurs and the
compound is colourless

LIMITATIONS OF CFT
that anionic
T.glnaTsexe andgsreatestP itiong'hEff'untied
Does not account for covalent character of
c.tt muteh prediction
bonding between ligand central atom

limitations are addressed by Ligand Field Theory and molecular Orbital

Iggy
NATURE OF METAL CARBON BOND IN METAL CARBONYLS
Dual Bonding Character

T.amfandI m Patient Into vacant orbital of metal atom

I pmlttat.IEenII sasprotledmdetan b
orbital donated to orbital of co ligand
n creates a
FI istttgtne gin9t naTe9iett in 9g1
APPLICATIONS OF COORDINATION COMPOUNDS

POINTS TO KEEP IN MIND FOR NOMENCLATURE