COORDINATION COMPOUNDS Heteronuclear complex :

more than one central atom

.

-
04 -
1H20)y 9 · - ColH2Oly 150412 Homoleptic complex
-

same
type of
ligands
NH2 35
↓ CV(NH3)6]
when two simple salts Molecular addition compounds
-
or more are or

mixed and
crystalised then
t G Homonuclear
complex-only one

3+
central metal
4
addition compounds are formed
. [CV/NH3la (H2O) 2) F Heterolytic complex
-

Different type of
ligands
KCI +
MgCl2 + 6H20 >
-

KCI .

MgCl2
.

GH2O some importent terms

- > 3+

carnallite
[CoINH3) , /H2012]
I
L
is stable.
Double salt K2SO4 +
Alz(SOn's + 24 H20 >
-

K2SOn Alz /SOn's.

·

24 H20
Perfect complex-where complexion
Potash alum + 3-
Stable in solid state but Ks[FeICNs] -3K [FeICN) , ] co-ordination polyhedron arrangement of ligand in
+
space.
-

dissociates in state FeSOn +

(NHulz SO4 + 6H20 >
-

FeSOn /NHulz SO4 GH20

.
.

aqueous .
M-Metal
L-Ligand
Mohy salt
Give the test of all ions Imperfect complex where
complexion is not very stable
. -

. .

co-ordination sphere ML2 L >

Mc L Linear C N 2
KCI
MgCl2 GH20 + = -
. =

K2[Cd(CN)g] [Cd(CN)g]
.
.

T -2 K

&
+

co-ordination compounds Non-ionisable part

"Mo
L
Ionisation sphere <M
-

stable in Both solid as well as

ML3 L
Trigonal planar C N . =
3
Ionisable
part L

*
- state > co-ordination
aqueous .

+ ve test sphere ML4 L L

Squareplanar C N =
4
.

Does not test of its ions

give the
-

K3 [Fe(CN)6] Co-ordination number

.

in
· co-ordination M
Ionisation Number of lone
ku[Fe(CN)6] L > number
pair accepted
sphere central Ligand - by metal atom/ion.
Denticity Hub
metal L

Number of lone pairs donated .

by ligand n

te
4kt , [Fe(CN)6]-
test ·
Fet2-ve test I
L
ML6
L
JV L
L
Octahedral C N .
=
G

I
Bidentate
Monodentate -

Donates 1 LP central metal

7
M
N
CN--ve test
M

L
Bidentate -

Donates 2 LP accept electron

Ligands CH2-CH2 ethane-1. 2. -diamine

Tridentate Donates 3 (P
-
> Lewis acid electron donors NH2 He diamine
or
ethylene
-

d-Block element
Pentadendate generally Lewis Bases

NITESH DEVNANI
Tetradentate Donates 4 LP
.

O
3
d
-

Pentadentate Donates 5 LP diamine tri acetato (EDTA)

Ethylene
-

O
-
0 Oxalate
M2N-CH2-4-0 Ambientate which have I donor site but can
-or glycinato
-

Hexadendate Donates 6 LP Tridentate C2042-

-
-

CH3CO0- CH3COO-
I site at
donate from a time
- Diethyl triamine !
.

-
I
N-CH2-CH2-N
- CNSCN' NOS NCNCS ONO
H2N-CH2-CH2-NH-CH2-CH2-NH2
-
· · a co
I
H CH3COO CH3 -C N
>
=

Hexadentate -
! dimethyl glyoximato
-
> Tetraden date

Ethylene diamine tetra-acetato (EDTA)"

-

Triethylene tetramine
CH3-CIN H
Flexidentate -

which can
vary denticity
=
2

acetanateo Sulphate 504

CH3 COO- CH3C00- NH2 CH2 CH2-NH-CH2 CH2-NH-CH2-CH2-NH2
acetyl
CH3-G-CH G-CMs
=
- -
-

N-CH2-CH2-N

CH3C00- CH3COO-
@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194
COORDINATION COMPOUNDS
Pd with C N form
Pt 4
always square planar
. =

complex irrespective of
ligand.
some
important points
[P+ Cln]2-Square planar
Neutral Cationic
[PdINH3) < ] -square
planar C
- Drawbacks of VBT
of the central atom
Naming a) Doesn't explain colour of compounds
H20
-aqua PPH3
-

Triphenylphosphine Not-Nitrosonium 6) Doesn't

distinguish blw weak feild ligands and
↑ Metal complex is cationic or neutral complex is anionic
NH3-ammine NHs-NHc Hydrazinium strong feild ligands.
*
-

Pyridine chromate
-

Cy Chromium
co-carbonyl NOT -

Nitronium
c) Does not
give quantitative interpretation of
MR
Manganese Manganate magnetic data
10-nitrosyl N .

CH2
CH2-ethylene NH2-OH
Hydroxylamine 4 ↑ Fe IVON Ferrate

& Bonding in metal

carbonyls
=
-

(
Co Cobalt Cobaltate

Anionic
Monodentate ligands Ni Nickel Nickelate
W

I
Cl copper cuprate
In ZinG Zincate Metal and carbon
sigma bond is formed
by donation
X
-
Halido N3- -

Nitrido Hybridisation
Ph Palladium Palladate of
carbonyl carbon into vacant orbital of metal M .

F- Fluorido NH2 -
Amido Sp-linear
Effective atomic number It Bond is formed
Carbon sidewise
Pt Platinum Platinate Metal and
by
CT-chlorido NH-imido sp2 -Trigonal planar
carbon.
EAN Atomic number Oxidation 2 Co-ordination Aq Silver
Argentate overlapping of M and
carbonyl sp3-Tetrahedral CN 4
Bo-Bromido N5-Azido + X
= - =

Gold Aurate
↑

All
I -

Iodido CN-Cyanido number number dsp2 Square planar

-

C N
. =
4

Mercurate
Hig Mercury spid -Octahedral CN =
6
On-hydroxido NC-Isocyanido Ti Titanium Titanate Outer orbital
02 -

Peroxido NO -

Nitrito-N complex

chelating ligands Oxidation number of metal is written just after the

d
Sp3-Square planar CN 6 =

O2 -

Superoxido ONO-Nitrito-O naming

↑

C
of central atom in
Inner Orbital
complex
Bidentate or
polydentate ligand woman numbers
.

5032- -

sulphito SCN-Thiocyanato-s which form chelates

-
can
(ving)
Thiocyanato-N
2
NCS
-

Sulphato
-

504
-

Increases
stability complex
of
Tetra Cobalt (III) M-amido-M-hydroxido
aqua
2
-

-Carbanato weak feild

CO3 ligand
co-ordination number No of
ligand x
Denticity tetra ammine chromium strong feild
ligand
-
.

O and
Halogen are donor
-
and N donoy
(III) Sulphate .
c are
No
pairing High spin complex.

NITESH DEVNANII
-

equal to atomic number of next Pairing if

required Low spin complex
-

If EAN is
OH

↑-
nearest noble then that complex is stable
.
gas Some special compounds (H20) 4 CO CoINMely (SO4)2
Applicable mainly for metal
carbonyls .
NH2

↓ theory- >
Valence Bond theory
↑

↑ IUPAC Nomenclature Werner's

Ligand donates lone pair to vacant

- Name of cation is written first and then anion Zeisse's salt KIP+ Cls(n2-(2H4)] orbital of central metal .
↓
a)
Sidgwick EAN Rule
.

Diamagnetic-colourless
6) While
writing complexion ,
name of
ligand is
Paramagnetic-coloured ,

order d d
written first in alphabetical .
pf CH2
Dipole moment - M V+ 21 BM Primary Valency (PV) Oxidation number
-

c) Prefixes di, tri etc are .

used Cl

Secondary Valency (SV) Co-ordination number

CH2
unpaired
-

n = electron
Note : If names of
ligands already have words
like bi tri, ,
tetra then we use special words

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

like bis tris tetrakes are used
, ,
.
COORDINATION COMPOUNDS
Stereochemical series of d-orbitals
Types
& BO SCN' Cl 92 <OH-cOx2- < d
< < < < < F
Non-axial-day dyz
Ik baar Sachin class favar oxalate ka
se or
Axial-dx-y2dz

Synergic Bonding. colour of compounds EDTA"- < Degenerate orbitals

Having some
energy
-

H20 < NCS <

NH3 < eR < NO2 < CN < CO

Paani Nachte udta Ammonia in North canada columbo

Y B CFSEX 1 x Xem
hue mila
-)
G
Xat sepyaar
i-acid e
ligands Ro Y
C-Donov > NDonOUL O Donor >
Halogens Trans effect
[Ni(H2O)6]2+ [Ni(H20) <(en)]2 (aq)
+
2H20
en
(ag) +
=

Effect of
synergic Bonding
-

Green Pale Blue CN > CO > NO < Et > PR3 > H > Ph > NO2 > I > SCN >

Metal and carbon -

BO4 =
BET =
BLU =+
[Ni(H20) 4 (en)] (aq) + en
(ag)
=
[Ni(H20)2(en)2]" (aq) + 2H20 BO > Cl >
Py < NH3 > OH < H20
carbon and BEX
oxygen-Box BL4

>
= =

-
Blue/Purple
chelating ligands are more stable than
nor-chelating
-

More the-ve
charge on metal [Ni(H20)2(en)2] "(ap) +
en(ag)
=

[Nilen)s]2(ag) + 2 H20

Violet ligands complex.

More is the
synergic bonding.
More the ON of central atom more is the
stability.

Crystal feild theory

-
Interaction blw metal atom and
ligand is
purely
-
I
tetrahedral
electrostatic. crystal field
splitting in
complex
-

Anionic
ligands
and neutral
are considered as
-vely point -
L Crystal feild theory
-

Ligands approach from blw the axis.

charges ligands as
point dipoles. L Non-axial orbitals face more
repulsion.
-

Different d-orbitals face different

repulsions and
↓
-

I
Non-axial
hence loose
degeneracy At
Crystal field
splitting energy
=
.
tz
octahedral complex
crystal field
splitting in

-
of d-orbitals
Loss of
degeneracy leads to
splitting
-

n
N

+ 0 4 At
Factors
affecting CFSE
.

In octahedral
complex ligands approach
,
towards axis
. At

NITESH DEVNANI
V

centre- - - - - - - -

Axial orbitals face

repulsion.

15degenerateoobiatse-
-

more
Oxidation number of central atom
-

0 6 At
.

Axial
CFSE 2
How to calculate [Fe(H2O)s]3 +> [Fe(H2O)s] 2 t

Crystal field
splitting energy
as
Ao
lg
= W V

-
.
M
N
l

Geometry + 0 .
6 10
Axial
6 A0)
(c) (yx 04 A0) AO
CFSE + +
x + 0
up Octahedral Tetrahedral
:

degenerate orbitals
- .

5
.

centre -
em
ligand (
↑5degenerateoobitaa
(in absence of
= No of .
electrons in
lg orbitals. Ligand E4
-

0 4 AO
.

No of electrons in
tagorbitals
More the
strong field ligand > More is CFSE V

1
-

At AO At
~

Note
y . 10
= .
.
: =

tag
Transition metal series . Non-axial
p pairing energy
=

degenerate orbitals No tetrahedral complex

pairing
5 -

in
number of 3d(4d < 50 (in absence of
ligand (
n
pairs.
=

Both for SFL and WFL

&' &2 d3 do d' d' >

-

same for SFL and WFL

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194

°
d"d5 d d >
-

diff for SFL and WFL

↑
COORDINATION COMPOUNDS
Isomerism
Linkage isomerism
C N
.
= 4 Tetrahedral
cis-platin-cis[Pt(NH3) 2C12] Wilkinson
catalyst
-

[Rh/PPhs)s(1)
Anti-cancer .
Hydrogenation of alkene
>
ambidentate
Arises when there
ligands.
-

>
are
-

NOGI
structural Stereo = 3-
[ColCl) + NOz] [Cr(C1) 5 ONO]
-

formed
Hydrate Geometrical
of
only in MABCD

Linkage Optical C N . = 4
Square planar

-
Jonisation
NO OI
and dissociation constant
stability
↓
Coordination Ionisation isomerism :

L
Arises when counterions are different
. Dissociation constant = 1

[Co(H20lyCI2] ] [Cr(H20l , CIIJCI GI Present B

- 7 constant
~
KI K2 K3
structural Isomerism B X X
Stability
=

Man NO GI

value of
Higher the B More stable is
complex.
=

MAzB NO GI

I Co-ordination isomerism

Arises when both cation and anion

:

complex
MA2Ba

MAzBC
2 Gl

2 GI
Hydrate isomerism are

water molecules
acting as both
ligand and In this
ligands or central atom is
exchanged MABCD 3GI Optical isomerism

water of [Co/NH316] [Cv(Cl)6] MIAA) 2 NO GI

Crystallisation.
[CV(H201s] Cl3 [ColH20) 5 (1) C2 .

H2O [CO (NH3) g] [CvlCl) 5 NHz]

-
MIAB) 2 2 Gl

C
L
L 7 Case 2 : Bidentate
->
-
Geometrical isomers
case-I -

Monodentate
ligand active
Stereoisomerism General Formulae Total wings = 2
optically
-

monodentate
Mabcdef 15 = Total diff .

ligand except trans-[MIAA)cB2]

NITESH DEVNANI
Mazbade 09 3
always optically active
MIAA)s -

Active
. I-occurs
G Because of different
angle
Mazbacc Of Except Maybe
MIAB)s -

Active
0 I- NO POS Or No COS MazD2C2 05
Manbz Inactive [Colen)s]"- Active
.

x =
2

metal atom Masbad 04

Terminalogy - M
[CV(gly) ]"
=

Ma5t x =
2 Inactive -

Active
:

A BCDEF-Monodentate Ma3OzC 03
Maz02C2 x =
3 active cis-[M/AAI2B2] -

Active
Maz03 02
AA-Symmetrical ligand.
Bidentate
Maybe x =
3 Inactive Cis-[CO(AA) 2B2] -

Active

AB-Unsymmetrical Bidentate ligand .

Maybe 02
MazbaC x =
3 active Trans-[M(AA) <B2] -

Inactive

Ma4O2 O2 Trans-[CO /C20412Ck] -Inactive

Mast Nil

Ma6 Nil

@niteshdevnanichemistry niteshdevnanichemistry niteshdevnani194