COORDINATION COMPOUNDS IN-DEPTH REVISION

Coordination
compounds
↓
Types of salts ↓
salt Double salt co-ordination
simple
Nace,K4 K2SO4 Al2(SOn/s 34420 complexes.
↓20 kn(f(CN1s]
Ho D. sn2", Alt 3

Nc,
↓

↓
H20
2

k4[F((N)s]Y-
+

they giveintent
will 4
+

ri g and)(secondary valency)
en -> co-ordination
sphere.
ieis]-co-ordination
X
no

d. central metal atom/ion

Primaryvery
 central metal ion
The metal ion which
form complex
anion, neutral molecule
with
positively charged
or ion

is known as central metal ion (CMI).

In central metal
general
* ion acts
as electron

pairacceptor co-ordinate
& bond with
forms

ligandssome times italso donates the eve the

to

BackBonding) Synergic Bonding).

ligand.
Its in

sphere the
on
central metal ion (CM2)

attached itare
ligands
of the
directly collectively
to

teemed as co-ordination sphere.

square blackets.
Itis written
in

bracketi s
part
*
The outside the known as

primary valency able.

are Valency(n] You
 mand'cutral/paritively
charged/negatively charged
ion molecules which combines with
cm2
form
or to

complex as called
ligands.
classification ofligands
↓

Denticity
crigancy)
attage .
electedin e

ligancy?
oredentely
or

by single
donated
The no

of
love
pairsof his a

ata time called

ligand denting origancy
is
①
ligand which
Monodentate
donate
can
re-pair
at a time.
-
; I" in, in, i, i, H,

, nO
e tc.

②
pysidine.
ddentate
ligandswhich can donate
se-pairfrom
differentatom/sites
two ata time

Leg cal
ethylenediamine ten). 8 oxalate
O

↓
(0x)

-
a
s d ..
o
of
azis

<3
1,10-phenatholine (0-phen)
...

o
 -
.
⑧
Il
(d)
auylacetonate acad Uz-Y-3

dimethylglyoximate (mal
-
En
A)
dipyridys/dry) -Emil
2.2

Il
(g) geycinate (gly)
r
③
ligand:-3 from pairs
Tridentate
-
lone at a time
atoms.
different
q* =
(a)
: name=?

4 -
-

T
⑧ (Dien):
Diethylenstriamine
-

-
MH2

ia*
④ hexadentate (EDTA):
ligand
ethylenediamine
tetra actate

- ..Uz--o
->
· &

I
-
&
- -
C -"M-m-a-o
--

1
a.
octahedral
#
-

Nat
o= kj
-

+
-
Amate
ligand those ligands which have

two
different for
atom donation
of
ets but

donate at
only
time.
can one
pain a

-
.
eg:
(=M:
- :N =

cyanide isocyanide
*-
M0 =
: N - nitrito(N)
nitrito (0)
-
- c=
N: -
--S-CEN

thiocyanide isothiocyanide
chelating ligands.
-

sing formation.
chelation -

polydentate ligand/biattachment
dentate ligands
*

whos

permits
structure the
of metal
two ar

more donor site

toattach to same

on simultaneously, loving sings

lating liganseg:(en)
one or more

are
 (incenly]
: Mat e
heM
--p
Nc
↳gegand: H
·

Me
I
-

me
of ligands of charge:
on the basis

①
Negatively charged ligands.
·Fu, b, In, m, si o2",
Eg =
oxide
su
seroxide
in, sin,
2
Or, etc.

peroxide
Neutral
ligands
②

8), CO,
it, no, en, dien, PHs PFs.

changed ene
③

biag nd
HN H3 hydrazinium ion
-
-
Benacceptor
of ability:
donor a -

⑰) which
(tyfe)
-orbital
Ligands
contain vacanta

thatcan excieve back donation

from mustal
the

io CO, NO, EM, NEC, RBP.:evacent

destital
Eg. !A
-
-

N 0.
= =N

M =
·

agree
ar
an

⑧ which do not have valent orbital

Ligands
to

recieve back donation.

MG F

Ligands having
②
having
but
no
compairof
X-bonding
es

-(ii) ><-
ziese's salt

1982
-
-
 co-ordination no.

=
(no of ligandsx ligancy)
k4(Fe(CN16]
(M 6x1 1
=
=

(ocenly)*(N 3x2 =
6
=

(PtUn]2* (N= 4x1 = 4

-

oxidation number:-Istate

no
Itis the which
sefriments
electric
the central metal atom
charge
on the

of
a
complexion.
 Homework
of following
①'Find CNCON
out the the
-

① k4[Fe(N(s] 1x4 x ( 1)x6

+
+
- 0
=

x 2
=

ON 2, (N 6x1 1.
=
=
=

② (Cu(N3)n]SO4

③ (Ni(0)n]

④ 1 2 (NiCCN) n]

⑤5
K
(AgEn]
⑥
(Ag(NH)2] OH

⑦ (((NH3)3U]

⑧
(Migey(z)
 co-ordination
of compounds?
-

Ruby
① I salts cation
is
first
common named a them

the
anion.

② In the acationic anionic)

complexion or

ligands
firstfollowed by
the
name
of
are named CMI.

③ The
by
indicated Roman numents
of
ON CMI is

after name
in the C3 the
of
CMI. The 2000

oxidation state indicated

by
is 101.

④ In neutral
care
of complexes, it is named as

one word.
(Nikoin]
tetractory(nickel (0).

⑤ should be
There
space bow the
name
of
cation&

the anion.
⑥
If
co-ordination
the
sphere is anathan
men

by adding
the is
of
name CMI written a

ruffix
in the metal.
of
-ate name

iron-ferrate Ag-
mecurate

Zincate
Age Argentate
In -

Al-Aluminate (r-cheomate

An-Aurate

⑦ ephers is
positively changed
co-ordination
the
I
then written
of
the name the CMI is as

such
 of ligands!
Nomenclature

I of
kinds
(a) there
are two or more
different
are
they
named in
ligands present
an then

affhabatical order.

4)
If particular ligand more than
a is one

is indicated
by
in the
no
complex,
times the

di+2
tri-3
tetra

penta
hexa
+4
-

-> 6
5 I
⑳ the (bi,-tri,-tetra
y of ligand
name contains
- -

then

I
bis-2
His + 3
th
tetrakis

pentakis -5

(Insen)z] is
ethylenediamine) sinc) ion
Nomenclature
of
anionic
ligands:
-

general
In
of ligand by
name
the written
is

suffix semoving fe
'o'a
adding
a

↳hydride -
hydrido
62--oxide ->
oXO

02"->
peroxide peloxo
-

oil
hydroxide hydroxido
- -

=-
fluoride flusido fluc
- or

vi-chlorida-chlor or chlorido

- Blomide - Blomo or Bromido

-
= Iodide- Iodido or Iodo

-canids- canido cyano.

or

NO5- nitrate - nitrato

NHScronandchattina
to
 neutral
-of
ligands.Ingeneral neutral

change
with
special
ligands
name do not some
name.

120
aqua
->

NH3 ->
ammine
-
-

castory
co-

witrys
No -

- pyridine

methyl
cy-Nter- amine

diogen
Oz +

Pts-phosphere.
CYH2
ar
C2-NH2 ethylenediamine
MHY-NH- wee
 Bonding incoordination
① VBT valence Bond
theory
-

②
LFTI cystalfield theory
CFT

③ (not in
syllabus)
↳gand field theory
①Bond
theory:
(VBT) -
hybridization.
CN
hybridization shapes
2
sp linear

p planar (nigonall
3

x I
4 tetrahedral

dsp2 square plans

tetrahedral
d3S

appe trigonal bipyramidal.

5

* spd
a
sp3
octahedral.
 Types of
orbitals involved in
hybridization:
-

sp3 -
1,px, py, P2,

sp2d s,px, Py P2, d22

->

/sp'd e
s,px, PY, P2, d23 drzy2

sp3d =>
S,PX, PY, P2, dazy, d22,
dy
dsp- dary2, s,px, py
des d2x,
dry, dyz,
a

(a) co-ordination 6
VBT
for no =

octahedral
*
complexes are
formed.
① (FeCl)" strength of
donation
of
es.

c-donors) M-donors 70-donor)

halogen
↳
donor.

[N, c0,7 MH3, en> HO, RY F, G, BvI

4 -

(FeUs) - C.N 6.=

ON=?
x (
+ -
1)x6
=
- 4
x =
+ 2
 35?3p!,
ester, 4s, 3d'

(A0)
26Fet2= (Ard
3d 48 4D 4d
12 1+()+
+
xX xx(xx x x x
x x)))
x

Gangy
sp3d
2
Lit ii ic
-
-

it
field ligand.
Since is a weak Itwill notcame

ee

magneticmoment infants i
42 4.
of unpaired
es 4 b
=
+

no
=
= =

nature
paramagnetic
->

that
pairing
* Since the did not occurs means

The
#
complex is outer obital
complex high spin complex
Lewis)"Ei
strong field ligand
② is

pairing of
(N 6
=
cames e.
Fet=GNE
 6
Fet2= (Aul 3d

& ↳S 44
12 + (4)*
+

I I

12/4/42(xxxx
- x(xx)xx
x

i Ein x
hybridization dsp3 =

orbital
this
i s inner
complex/low spin complex.
paired
why diamagnetic.
Since
* all the
ears that it is

u 0.
=

③ ((H201634 (N=6,
H20-weakligand.
24C (AU) 4s',395
=

24(r+3 (Ar] 3d3

=

3d ↳S 4p ↳ch

⑭
(x xX
xx/xx)xx 111I
inner obital
vint sp- complex.
u x553
= 2) +
T5BM.
=

oh-palamagnetic
 system:diepI
d'ed2
*

(sc(H20Is] gisat= lAr3d' paramagnetic

u 15BM.
=

By configurationis didwecan ofdinate

the

no

irrespective I ligand
Home work:
-

* (Fe(N1s]3: ->
hybridization=!
u =
?
inner
orbital/outer orbital.=?
low or
high spin =?

(NiCHeOls]=aNit= (Ar 308

⑰

124442k)4 xX xx)xX
x x/xx11
-

l =
BM.
Id?

palamagnetic
=
n
=

(Ni(N)s]
MM-strongfield.
20NitE = (Ar) 3d8
 Ni2= (Ar 3d8
&
124442414 X
x x
xxxxxxxx)))
↓ -

!
the spid2
pairing with
d not
posible
paramagnetic
d4,d5,dS

valence
* Bond
theory for (N=4!-aquan plans.

↳ sp3] -
id

*
① (in) Ni =(A01398
field ligand.
↳ weak

12/12) 42) x) x)xx

*s
+
x
-

↳b
e 18BM.
=

#3
palamagnetic.
② (NiCNn]2
strong field ligand
↳

Nit =(A308

(21+2+ 2/44 ->

diamagnetic
12/H+2/2xx1xx)

planat
special cares -

[xi(014] Ni (Aul
=

308,452
⑳

Ge ↑2/14+ r)4 12 11

trong field big

and

12/12/12/12) 42 x* x
x
xx1xx
sp- tetrahedral
diamagnetic
--

O
special cave-2 (CuINsIn]*=Cut2 (Ar13d9 =

and transference
3d strongfield Ling upto -
-

12(+2)+2)+2) 11

12/12(42(2)xx xX x
x/xx) +

-square planar
u 23 =

(cury)=?

errence:
shifting
Itis the transfer of
or an election

higher
level level
from lower
a to
energy energy
a

in a
complex compound when the
following conditions
are
satisfied! -

⑪ be
only one e can
transferred.
②
strong field ligand.
Prense
of
posibilityof formation of
③ There should be inner orbital

complex.
Drawbacks
of
VBT: -
 the
↳meld
oy
metal ion & both point
orbitalligands
to CET,
According
an

and is
there interaction on metalion
changes
no

the
ligand.
and

the
five d obitals are

duy, d23
,
da
↓
in between the axis
along
axis
the
Y12/X 2

& 2
&8 "
da-y2 de

CFT

↳ -

Octahedral Tetrahedral
Squan/lanas
complex complex comfelixes.
* octahedral
CFT
for complexes -

isthe
ligands, an approaching in
an

the arbitals which

fore those
will be
all

more. along
the
axis
repelled
dxy2 d22

.......
-
too--I -

0.4Do
ID0 10DN

units
=

- ant

is
axydyzdext2g
(Fe(CNs]"-
Fett (Ard
-
- initial
tagh egh
-
before pairing

--F_qq after
Namition

did transition (pausing)

↑+14
try go
 stablization
crystal field energy
abtal) x -0.410
CFSEOL
(noy esinty aktals) x(-b0) Po
=

nog esineg
-
+
Y Do>4=then
pausing
will occur.
pairing
<P then will notoccus energy
pairing
Do is

② Tetrahedral
CFT
for complexes:-

~* - Ligandsasapproaching
intere

- theenergy ofthose set

at
i a

will
axis be more.

I
in ~
day dyzdex

'
1,
X...-- I -
--

↑- 0.61t

I
axy2 d22
Remember
4
At =
Do
this
F
Dz
&* Do How?
explain.
= = >

tetrahedral complexes:
CFSE
for
-

introtital)
Loges in eabitals) x40.6B1) hoy0.4At)e
CASE =
+

x (+

CFTfor
square planar complexes.-
22 LI

--
i

--

d22-ya
↳3 ↳
du?y2

, X...--
axyaizazitayz'azx
 Spectrochemical series'
weakest
-
< Br< <u- <N85 <F- <o<EtoH<20n2
NO2 < IN <CO
Pysidine
H20> EDTA > NHy Len >
-

strongat
it
affecting magnitude of f
crystal ield epliting
Factors the

①
oxidate state metal
of
ion!

oxidate state metal

magnitude of splitting energy 24
of
(CoCMM3)s]> (Co(N3)0]
+2

(FCCN)s]-> (Fe(CN)s]"-

of
ligand-
strong fieldligands
causes more

eplitting compand field ligand.

as

34
(ots) ( [LoLHro)s] (((o(NH3)6]
↓ ↓
sp3d2 asp?

⑧Fresentof heatingliganderchelating ligand ane

(cocenls* > (Co(MH3)6)3+

④ central metal ion'?
ty
of
3d 3d 4d&Sd uries.
ad
among
5d CESE is most
50>4d<3d.
for

"

Nica)*< (9dUn) (PtU2

ep3 dsp2 dsp2
colours in the
compounds?
Reasons
for colours in
compounds
I did transition & Resonance or delocalization
of es.

③ metal transfer.
ligand charge
LMCTe to

⑭ polarization

⑤
HOMo-LUMO tramfel.
change
⑥ F-centres metal excess
defect
 =x
⑪ Aransition

color wheel!
-
- has abated
R VOI If a
compound
-
the
will emit
green
led
light it
then

G
y

light
*
Y is
CASE more
wavelength
hall be less
of
abated

highes
I will be the emitted
wavelength of
radiation.

② metal
Ligand charge transfer:
LMCT - to -

- -
-

+7

KMO4 g5Mut
=> =>
102,252,2p%35?3p3
↓ ↓
link
apple hybridization

I
or,
in Sanders
-

o 82
-

eg:lacanno
Blue.
-
-

ele
③ Polarization."
to
(polarization)
AgU,
↓
Agr Ag?
white palyellow Bright yellow
④ transition:
Amo halogens are coloured.

U-greenish yellow
Brz- Brown (Reddick)

Is - violet

of complexes?-
y
affecting stablityof complexes:-
Factors

①E: Greates the CFSE

greate will be the
stabilityof
complex
② central metal ion
charge demily of
demity stability-
a
charge
③
Ligand
of
strong field ligands form more stable

complexes.
④ Chelate effect:- chelation
quate the
greater
will
be the

stability
atomic no):
Ruler
⑤ -

nearest
attain the
complexes
In CMI tends
the to

configuration by accepting
the
donating
noble es
gas
or

EAN = 2-ON+2xCN

2- atomic no

on-oxidation no.
CN-co-ordination no.

IV016] =
oxidation or reduction

23 6X2
+
E
(rK01]
25
=
 Isomerism in co-ordination
complexes
I
↓ I
structural stereo

f
-

->
Ionization

Hydrate ↳
geometrical
optical.
ankage
->
co-ordination
steless
co-ordination
->
position

al
Isomerism:

① Fonization isomerism'
The
compounds having
same
emperical formula producing
but
different ions

solution called ionization

aqueous
in the as

(the
getexchanged)
isomers.
primary secondary
& valencies

[Co(X3)5 Br) SO4 [20(X43)5SOn] Br

20 20
↑
↓

(Co(N15 Br] sOn2 (Co(Ns)5SOn] Bu

↓
↓AgNO3 AgNO3
Agesone yellow
② Hydrate isomerism?
compounds havi n g
The same

empirical formula
but
different of nomolecules
of
120

of hydration
called
an
hydrate isomers.

(CrCH2OJoJUs -> violet color

[Cu(H20)5U] U2 H20 -
Light green
(Cr(120) 442] 4.9420- dark
green
X(Us]-3HO- not exist

↓
neutral hold
by
to cannotbe
->

neutral
species.
③ isomerism:
-

Linkage shown
Linkage
isomerism is

ambidentate im, NOz, sein ete

by ligands eg. +2

1 I
27 NH3

oxewns ⑭01-13
BM s iM *s
④ Esomersin!
co-ordinationSphen
-

which
compounds
The

have cationic & anionic

both
part as
complexshow
this
type of by exchange of ligands
isomerism the

bw them.
↓
cation
↓
anion

[Nels] (CU(KN)s]
+ 3
+

C [col2a)s]" (Cr (NH3)6]

3
+

->

anion cation

[Cw(N)s] (Co[cas]

⑤position isomerism

Itoccurs when
ligands
have
different positions
central metal ions
polymadal
wort the two in a

complexe ([NA37420CCHoin) (son)2

(120) (X437s coYcCrols(N)]sona
 isomerism:
2
① co-ordination
of
In care no: -4

(a) Tetrahedral
complex to complexes geneal
in

show
ligand itlf
do not G.I. untill & rules the

Show G.I.

⑥ Square planal complexes: ange-

90" is form
(9,6) (a,2)
-,a (2,a)(2,d)
M (6,d) (9.6)
d
/ -
180 trans
(C,6) (a,d)
=(d,a) angle
-
from
(216) (a,d)
a 9
2 /
* X NO G.I.
Ma4 -

af
in
-a

6 9
- X G.I
May6 -
M
-
no
a
a

A 6
M9262 6 -"
-

-
M -in (2a-=)
↓
a a -
in trans
-
-
 a 6
M926C a
-6 -
M in

a l a
(a,2)(a,b) (a,a)(6,2)

Mabed

A d
6 a
-
a
- - /
- i
in M
-
d c ↳y
a C /
(a,)(d,6) (9,d)(6,2) (9,6) ((,d)

MCAA

Em *) no
x Gf-

↳possible
m(AB)z

i m C
-
-

-AB)
(AB) (BB)
 in octahedral
endomerism complexes:-
M96
9
a
- 1/9 x no G.I.
M
q
a
, optically
inactive

M956 a
6 1/9
noa
- X
M -

all
- in
a inade

Ma462
6 6
a I a
a
- 1,6
as M M

1- a
6
a
- a

(trans) (a)
inactive inactive
Mazt3
optically optically
a ·" a

6
1 a 6
- 1,6
M
ofpically
-
a optically
inactive
↓
a e

(916) (916) (9,6) > (a,a)(6,6)(a,b)

(fac] (facial isomer meridonial (meel
 M926,2
9 C

C 9 -
6
C
- 1,6 9
- 1-6
- M M M

6
!

-
c a
6
inactive
optically 9

"
6 9

-1- C
-
1,9
in
a
C
- 5 -
-
a 6

no POS
-
NOCOS

active
non
super imposable
optically mirror
images.
are called
(they I
Matedef enantioners
-> 15

A_1_A
-
M(AA)3

④ Cr
M

a -
-
Al
exmeltin
-im -
Ministere i bA
-
-
-

2 2
 M(ABIz

:B
Al
C
--
M in

a
B -B
(AA) (BC)(BC) (AB) (AC) (BC)

AL Al

i
1
--In - B

Y
-

!
AA)(BBIC2C) (AB) (AB)(C) (ACTAC) (BB)

M(AB) d
c 22

A7 Al
de B d --

·YMa
M M M

a a -d
C
C d

-- -
M A) -3)
a
dA
-
a B

di
Hapticity:M).The total
of
in the
ligands
no atoms

which donatable
belongs
to the F-ecloud is

called
hapticity.
[ xe
belong
to 6
calboney.

)
4=L:
⑳
nogre

I itYet (insezcanal ass

] Fenlocene
Sandwick
-
compond

⑰ (cysns(z)
carbonyls:-=
2
Co is a donor a
e-acceptor.

⑱-Geo
Due
synergic
-
to

bonding
in Bond

become
very strong.
strength of backbonding
be
The can
compared by
*

following factors:
the -

①
oxidation state metal ion
of oxidation
Lower the

greates
be the
demily
state will electron
of
CMI

metal
grate
on the a hence will extent
be the

of Jack
Bonding
of backbonding strongerwill
Greate the
* extent be
M-cBond & weaker will c-0
↳
CO band deckae.
of
Bo
Bond increase.
Bondlenth of
CO
 (in[01] (in(ois] (inn (2010)
(a) ⑥ ② X

of Back
Bonding
extent : -
> 67a

length
-o bond - >67a

-o bond order +
a76>C
-

② the oxidation state is

y
same
compare
then

Hileft
gher
weaker will be M-C
self of cr1.
= @ x= π- >

Backbonding
be
& smaller will to bond
length.
(Co(0(u) (Mik07]
Back a>6
Banding
Extent
of
->

as 6
c-o
Bondlength -
--
 calculation
of
bonds in
of polynuclear complexes
no in-i

bond
(2012(2010 -
no
of
co-Co

E dicobalt
calculate octacalbory)
Total
* valence in the
entire molecule. (i.e., the

&
of valence es
of
metal
of from ligandN
each
no no
-

charge).
-

substractthisno
from (nx18) where is the metal
*

of
n no

(4x18)
ions
complex
in the =>
-
A B
=
->

I gives total
the
of
M-M bands
complex
in the
* no

(2012 (CO) 8
27
=
(Ar13
A 9x2 8x2
=
+

18 + 16 34
=
=

B
(18 xn)
= -
A

(8x2)
= -
A 30
=
-
34 2
=

noo Bands
=
co-co =

= 1
 ·cool
(Mnc(0)10) A 7x2 2x10
=
+ =

34
B (18xn)
=
- A

18x2-34
=
2
=

roof ===I
bonds

CO

04 I
CO

o in-in

loo
-

C
-Lo
(RUU(PhP)3]
catalyst
Wilkinson's
↓
hydrogenation of
alkenes

chain
of
double bond at the
end the
is
hydrogenated
butdouble in centres
bond are

-
affected.
not H2

-
X
 Ziegles-Natta catalyst: -hetrogeneous catalyst
(C2HsgAL+ TiUn]
It is
for
tied low
temp-polymerizationof
alkeve

for HDPE -

high densitypolyethere
from etherne

ai-platin:
-(Ptolaus te
I
agent
- beaten
cancel.

*lead
poisoning by
in the
body
can be removed

form of CGHzEDTA]
EDTAin the

fetz ret

Haemoglobin oxy hemoglobint

-
-

cheophyll ->ing+2
vitamin -cot2.
B12