Coordination compds

af.com

double
salts Cada ka 6h20 cat It It E

Ngos Caio
Mft Cath

salts 3kcal refix Kt Tets

complex
I

primary valency
complex sphere Danioni
37

gation sphere coordination sphere

coordination Number

Central metal
atom ion CMI
I or Con
C

a ligands Secondary valency of CMI

rich species which donates donations

of

e no e

pair CMI

e
pair Ip or n bond accepted by
one

to CMI

a En

eight IE.gg

Mononuclear

complex É

only one CMI in EN homoleptic complex

one coordination sphere

only one type of ligand

species

É tmI

Not nitrosylium monodentate

MHz NI hydraginian
monodentate


Ii Neutral H2o aqua quo monodentate

ammine monodentate

HzN

Nine Nine hydrazine monodentate

co bidentate symmetrical
Carbonyl lent

yyychz stk.my

Not nitrosyl chdtingtigand

I d ethane 1,2 diamine

2 bidentate
Ey glycol

no symm

whack diet tridentata

ÉÉ

diethylenetriaming

mi

tetradentate
MEENA tsien

Nit inter

for

cha cha lethene 2 hapticity a ligands

FILED dipysidine

Idipy
Eft pyridine Py

monodentate bidentate

sym


It hapticity 2 6 is donated 6

2 e's donated 6

check Éiz Y 3 e's donated 4

Ui

Anion

MHz

f florido fluoro amido

2
Ce chlorido chloro carbonate

coz
Br bromide nitrate

Moz

I iodido soy
2
sulphate

n hydride

0
2
OXO 805 sulphito

g en

peroxo cyano

2 2
02 204 oxalato bidentate

peroxo 10 1 sym
2

5 sulphide

goo bidentate

NJ azido cha glyl

I unsymm

M 3 hitsido MHz glycinato

115 g
CI atty acan

o g acetylacetonato path
co
Cedtat

I I in cacoo
bidentate ethylene
I

symm diamine
6 mem chelation tetra
In coo

cha

acetate

Hz ÉC

hexidentate

P valency t2

S n en 6 100 Kz edta

otto

ligand edta Y

C sphere anionic
O EI t

CMI Fett o

shape s octahedral

goo
polydentateligands

N K N angles g
specially bidentate span

N r o
49 it

angles

smaller angles

co te o
47
angles

K Pta
Ziese salt

fatty

heteroleptin Pt t

sq planar shape gÉIÉ

anioni coordination sphere

Co

Nikola homoleptic

CN 4 f
Carbonyl co

ligand

tetrahedral Oc co

P valency ZERO
co

IS cen

CEN

thiocyanate s thiocyanate N

re Ncs

Belsen

go nito

g Nif

nitrito o nitrito N

nitrite nitro

Co Ono
Co Moz

Bridging ligands one donate 2 e to 2 CMI

ligand pairs

one donation to each CMI

polytplexes

In L

methm

im

it to if ti

Q How

many of these can't be

bridging ligands

Mine titis o

13

Nomenclature

ligand are alphabetically preferred

multiple ligands of same type prefixes



nora prefixes di hi tetra peta hea

Iganidig prefixes bis Is tetrakis pentaI

or
organicpolydentate

calais coordi sphere

if metal ion is in metal or

it

use
english Inane for

coordi sphere then

if metal ion is in Anion

its with ate

sometimes we use
Inane suffix

ferrate apperate Innate Irgentate

meat aurate plumbat

written in Romannot

oxidation state of metal ion is

Acids with complex anionic past are

differently

named

No prefixes to be used in ionization sphere

for ions

Kelty

Example

potassium hexacyanoferrate II

Naz
Éecini sci

sodium penta
ferrate II

cyano thiocyanate

Naz Colox 3

Sodium trioxalato cobaltate II

fictizo II soy Brownringcomplex

pentaapanitrosylium iron I sulphate

Naz Felin Nt sodium nitroprunide complex

sod pentacyanonitrosyliamferrate II

th o I

Pt Hz MHz SCN

zPOy

nsme am.me
tzth yando splatinum II phosphate

Leo
mmsm_aftithrgand honor

same connectivities but

orientations

connectivities diff spatial

isomerism isomerism

Ionization geometrical

coordinate isomerism

optical

Hydrate

linkage

it

Polymerisation't

Igizationisomerism

usually negatively charged ligand s are exchanged btw Ionized

sphere coordintiosphere

anionic cationi

gen gen

Same CMI Same OS both spheres must exist

Saa


Ptt Pt Mtb Cl Br

ans al Bra a Br

Pt NHK CBD Cla

PI

C.tk

Hydrate isomerism ionization isomerism

special case
of

where
only H2o moleculeIs are

exchanged b w two spheres one ionization

other coordi

Same CMI Same OS both spheres must exist

Saa

E fftHzolsIoiJClzVffefHzolaCnol yJcl.t how

tremolo tooth
No ionization sphere
o

an has changed

IetfI Nottz

0th

1120

o to H

Coordination isomerism

from one coordinate sphere is

ligand exchanged with

another

ligand from

both CMI maintain this OS CN

2 diff coordi sphere

Cotati pitta

Co NH3 3G Pt A g Mtb

Co NHI it X

a t flyable

Pt 63 Mtb Co Mtb
H

Pt G 24 34 CoV L

linkage Isomerism

due to ambidentate ligands

Linkage connectivity diff only

nature

Sai Noi

K2 Fe Nts say Inoz z

SS MN

II
K2 Fe Mtb

nestling

K2 Fe Nts Saxon

K2 Fe Nts z nestfomolz

K2 Fe Nts Sen Ncs Noa



K2 Fe NH3 Sen Ncs Moz ono

K2 Fe Nts Sen Ncs Como

K2 Fe

NH3 Ncs Moz ono

K2 Fe NH3 sa 25m02 ono

Polymerisation isomerism

Emp formula same mol formula

diff

PIC slice's Ptah YpÉ a y

Geo.Isomerist

120

Mhz took My
To 1 7
only

linear D planar

900 4

My 6
y y
180 4 109028 6
only
66

sq planar

tetrahedral

9a 900 12

MLG MA 1800 3

octahedral

1stcondith Two type

of bond angles at least

Miz Miz Mly tetrahedral do not show 9 I


2nd condition Difference in angle combinations must be possible

Sqpland

loyal

Ld I L

a monodentate ligand

Laal bidentate symm

my
label mm

unsy
and

No G E

possible

Id and 900 1800

No 9 E possible
2

18

ant 900 180

mat
jeg
ta
jeg

GMT 1800
but

900 only

only

Make Maid

geom

isomers

cygyoffBidentate

Remember to create loop or

900
chelation

angles only


M a M aa be M aa be

8 8

mens

geomisomen T no
geom isomerism

special case of May

city gestation

M a bb Ob no
geom isomerism

o Mla b ez

Mlable 12

Ém
91

Eng

FE

El Ia

no trans 7 not possible

Es trans

due to

not'ming chelationangle

M abl ed M ab ie M labia

2 9 I

no g I 2 9 I

msn.me

1 Ptt's 2 possibility

oganiigygandzpo.int

All Pdt Pt complexes CN 4 are
sq planar in
shape

Octahedral

Mac
a
Masb mi

b of

9 mum a No

No
HMM pm 9I
a a
g

I

a a

b b

Maybe

2 9 I b

a mania a mmmm

add a
p

b a

b b b

Magby
b

a
I a ba mm

m a
gym bad

a gg 9

b a
b

meridional mea
facial fad

Mazbacz

a a a b

a c c m ba c mm by mm a
gym or cap
KE

b c c

a b a b

all trans all cis aa trans bb trans

Mashed c

a b

m trans

193121 add

Mabdef
c Kanarese
8

O n

of

O 3 isomers

III If pyx

Mazbzed

Mlaalzba 12 10

M 9973 M aa z bb

a a

No G I

a a b M b

Ph E a trans

M aa bb cc M aa by
TGI

No GI as
only

all cis compd exists

Mala lbb cz 2
M aa baez

alla's bb trans co trans

II astray

13 9 I


1113

a a

by and

a mm mm b

ga app

b
facial meridional
a

M lab zCz

a a a b

bb

c m c n a c C M a

bbl TM gym

Ed

a b a b

all trans
alias aatrans bbtrae

man

cop acetran
a

Miabiled ef

O m

1 4 8

069 2 isomers

c d e
f

EAI Effective atomic Number

CMI

2x Ipdonations EAN

total e
fromligands

n e

from y 36 Kr

54 Xe

86 Rn

Fetting 26 2 2 6 36

Moz 27 3 2 6 36

33
Co

MHz 27 2 2

H2o not 26 1 2 6 37

Pilant zÉ cat

78 2 4 314 121 84

425 545

26 2
2161 36

ferry

FI EJ

on

Gandwich complexes aromatic

pnÉg

me isomers cheek of

Pos cos

Enantiomeric

pairs

Sepland No
opt isomerism about CMI

tetrahedral opt isomerism

possible

octahedral i

May Mazb Mazbz Maybe

PI PI PI PI

3 2 s
at

a
way

Mabid

i Post

P.to Y b b
Jfc
d
alfy

C a

Miaa bz M a be Mlas bb

Pos 2 POSA POSHI

100M able M lab cz Mlabled

opt active Pos along 2 enantiomers

b
I ftp

Enan

I
f

Mla b ed

a my 2 enantiomers

Octahedral cases

a b

Mac Masb

cos

post a a a A gagging i

3 axial

planes a

G in Btw 11 a a

no isomerism

Maybe a opt a

cos u

b Pos

post mm a
mamba

a as
both no
opt

trans

no

opt isomers isomers

Magby a a
no optactivity

POS 31 mm
tiff

no
opt
btl
fay

meridional
activity

b a

Mazbacz

a a b c

mi C mm b mm a a mi by

op ga car ya

a a b c

trans

all aatrans bbtrans cc trans

POS

aahiayII.ma.to

al

mm enan

Cory
C

Item

s
5
estbenannhenanmw
is

geo
z

opt

in
an active I

enan I

pairs b
diastereo

Cz 1 15 1

Madef

total stereo 30 enan 15

15
pairs

geo
iso diastereo C2 15 435 15

30
opt
a

11 an active
30

Mazbeed

d
I

enan t 9 n b i enan

mm b

i
i a of

add I

total r

geom

I stereo i 8

tone

Miaa Mlaalzbz

a
optically active enantiomers

a
i
a a marina b b

yay

b EI a trans
ah'm

a
a m a a y

plane conty loops

add

Bea
sifting

a f a

Eis

10

M aa z bb 2 than M aa bb se 2 enan

Mlaa by opt inactive

Mala bb cz M aa baez

a c all cis A a enan

bb trans B
y

no

C mm a a man's op

si trans isomers

ay add
c

b a
caltrans

no optactivity


cts hyenan

4 stereoisomers
GI 2

enan z
pair

Mfb opt active 4

a
dias 4

a
m
by mmmm
b

Eff b yo

b
facial meridional

M lab zCz

a a a b c

m c c a c
bb c a a n b
gym gym gym add
Mk

a b a b e

all trans cotrans

alley

03 É
i

8 GI

Miabiled ef a

10 OI

18 stereoisomers

O m
enan

go dias
pairs
1662 8

die f

pains

Bonding

shapes

octahedral sp'd desp3 day edge

sq planar 4 dsp t da

y d's
yr

way sp3 dry dyz don

TBP 5 sp'd dsp dz2

sq pyram 5
sp'd't s
day

CFI

Crystal father

Treat EMI election at origin

as point deficiency
Treat i i election rich species in a

ligands
around
symmetrical field

origin
Assume coulombic interactions b w CMI

ligands

Shape
of complex controls ligand field pattern strength

Field pattern can affect degeneracy of d subshell

PE

a Do splitting Energy

in octahedral

gap dry dz eg

field
1 ba.ge

04 Do

just before

splitting

in octahedral In day dyz.dzn tag

ix field

absenie of ext ligand splitting

field

ineld

tag
set of 3 d orbs day dyz dz n

lobaldensity inblwtheaxes


of 2 d orbs ineld is along

eg dayglobal density
the axes

dye

r
more PE due to Ligand

field direct intercom

7
octahedral

field of

a
80,608088080
page day

88
dz

In tetrahedral 4 ligands approach

field

along

PE

a Dt

in Hetrahedral
sphingygnergy
gap day dyz.dzn ta

I Is

ijE É

splitting day dz

my inftefghedral

absenie of ext ligand Dt 4g Do approx

field

approach vector are closer

to

ligands

set of orbs than to set

orbs Hence splitting is into 2

of fold

3 fold degeneracies


At 3 Do

TT
1
f

n 2
7
3 is the ratio 213 ratio is

of due to approach

ligandfield strength

as chat c angle diff btw

d orbital

lig

E dna

yr

Ii

r z

dz i
just before

yep in

taffetingand

field

factors affecting s

a CN 6 7 CN 4 7 Can

ligand quantity

same ant same O's same ligand nature

Ni thot Mi Ni tho

thole


b CMI OS

mon o S more D

same metal same CN same ligand nature

Affeltizo d re tho

diff metals of
c d series

sd series nd sends 7 3d series

generally

4ft v
poor

shielding 20 257 inc

40 50 in ing
00

in D

Loft J ex cm interms
of Il

d spectrochemical series L field strength

halides c o band N based E C based

generally

extent Mt's a en e dien c trien

of
chelation

Backbonding possibilities case

synergy bonding

ren complexating are stronger than a Cigs

ligs only

Tk I Br c ish c u s Nj s f s ott

99 0 into a 4344 C Py C NtlzCedt

moderate
endpyLmoico.pph en co

no

In of yd sd central metal atoms ions most

case or
ofthese

ligands feet as strong field

Aqua complexes

M H2o o All these 3d series complexes have 420 as WFL

M Holo All these 3d series complexes have 420 as SFL

except in Fet thot

Ice

we

frilly 1113 WFL Finola WFL

Nikola

retcon no SFL s SEL

Pfa

intis SFL Patey Skl

Pfau Mtb SFL RÉ PPh 4

2
SFL

do diamagnet al p Octahedral complexes

d I l

dodd paramagnet d i n 4 or 2

I d l n 5 or 34 or l

d n

at ii

da l
III X

i n

d8 n
WEI

FYI E X

Dory
h
Edd

Pin

wee

IE n

I g

d Ao dy si

171

O
MI

ie

M RBM M 85 BM

we M E n't

d I 1
tag ego tag ego

d2 I 2

tag ego tag ego

d 3 3
tag ego tag ego

d 4 2

stag eg tag ego

5 I

d l tag eg2 tags ego

o
4

d tag eg tag ego

dt 3 l

tags eg2 tag eg

d 2 2

tag ega tag egg

da I l

tag eg tag eg

d o o

tag eg tag eg

Sp all 3 subshells are valente outer orbital complex

d subshell is penultimate linner

dig

WE SFI

MI

FI Thi IIIesse gap Beth

my n
lower It tombe
Mone E

gap

It is d

ME Max

do d see dsp

do do we sp 392

d7 spl case

d8 d Stl wet sp'd only

t2 an oxidant 13

co mtg co mtg

cont lot d'T cut lot d tag ego

SFL I

ligand NH3 ligand MHz

ex 6 in 6

shape octahedral shape octahedral

hyb d's p't hyb d'sp3

complex inner orb compl complex inner orbital complex

n s I n T O

M I G B M M I 0 BM

paramagnetic diamagnetic

171 1

It her re
1p

My

Ga

Ga

Co Moz Moz spent oxidize

m2 t No t

LIFE36

EAM 37

Craig Te H2o Te CN

3ds

cats Itzgeg CMI Fet tag eg cont Fetz

care tags

ligand WFL ligand Stl

ligand Ntl SFL

en 6 in 6

gtfo octa octa

ch shape shape

desp3 hyb sp d hyb d2sp3

hyb

complex complex inner

complex

inner youter
M n T O
ml

E BM
M Fa BM
i M O
lowspin

spinfree

orhighspin spin free highspin spin paired

complex

Cre

complexes

If sp dsp

tetrahedral tetrahedral Sgplanar

the

gaff

Myat

gig
y
la

do d8 WFL 2 PT

Mnoy Mno Croy

0
d any L
Sp

natron Cruz Crone

da shape decides

nation Cros V05 decides

Mn207

do or d config

with v high o s on

CMI

PtCalzkitis PtdIns

Miely j

W FL o
SFL OS FL

f 98 eat tag odd To d8 To

BM

o sq planar sq planar

3
Eilat Nicola

Catena

SFL a SFL T SFL

d leg tag To o
dio eg tag d leg tag

tetrahedral o
tetrahedral tetrahedral

3d8y

Hiding 2 Blood red coloration Ni 3d895

magnifying

Mi
feta 3910
d8
II

man.tt

so planar

Bigga

00 Hy
i

nd

inexed
Lie tn

On I

3

t

a hit two er oma

d7 a
d d3

chest tetra WFL well tetrah

sqplanar dsp M 58 BM o
sp

BB M on 2 o
n 3

HI n

a

paramagnetic egg tag

inner
orbital eggtag

SFL

IT
China

y II St
D

blue to dsp
deep

complex Sq planar
AAAA BBM
É

Inerohital

Cactus Critias Latices Amey eaten

tetrahedral SE planar tetrahedral



SynegiaBonding

metal carbonyls a

organometallics

co sat not

Ig
ligands no
Igeptor

PPhy PF

M L is

r donation n donation

b w Lem creates rt M character

Synergy

R donation M L is also known as Backbonding

from

Me Ot normal r donation of Clp

0I

M got M C Back bond

Synergic bond

sty mocreahn

Mc CMO

C00 h_e.m c o

LVMH Homo Tmo created

stage

IB

08

creafn_Blw .i

ing

omo reduction in

B O
of Co

orbitals

ima
molecule or

if

unit

interaction increases due to both r donat

ta c

F accepting natures

More Back bonding Less Co Bond order

He

less streaking frequency 4 More o bondlength

streching of c

1.128 A

A Free

co bond length is

complex have

Almost all co co bond length 7 1.1288g

Strechingfpenyls Ft

I
s f a

free co

Backbonding in co sp less than 2143 a

whichcomplex
9
CAT

Creole
anent gives best
BB

1860cm
l 2000cm l gogo em
1

charge on CMI more SF shorter co bond

leff

or

Enfeticiency length

rank

Ti co 4607J Feds
Be

B B strength co bond length mic bond strength

is is decreasing is

decreasing decreasing

Bridgingcoligands

Mako Costco g
tea

to

CO CO

eÉ

OC

so co

26 6 3 36 25 10 3 27 6 1 1 35

1 dueto

f bond dueto

g M Mbond S M M

bond

Most of the times complexes to achieve FAN

values
try

of
36 54 86

Stability

old criteria was EAN

I is more due

II Moses
stability
more specially if

to strength of ligand

Xii Chelations more chelations more stability

Civ Kstability or

formation

Mt M Males leal Glen

Mhs male eat

Atti

MIMI t l en s M mens then 2 NH

MIMI 2 en s M renascent 4 NH Atl

3 talent G Mtb

Minato t en s Atl

Dni is almost same in all three reactions



chelation as DH values are small

is entropically favored process

similar
negative d4

or Hence increasing as ensures more

More chelation more O AG

MINH t 3 en s talents 6 Mtb

mi

MINUIT t 2 dien s M dien G nity a

Minn t edta s m ladta 6 Mn Atl

extent of chelation more

more
per ligand stability

in Kstability or Kformation

Mt nil Mln Kym Kformation

lag Cag lag

a Mt L ML k

lag Cag lag

b ML Lay I ML
2 K2

lag

nth Mln Tag

t
Lay I ML kn

h lag

Keim Ki ka ks kn
I Ki Bn formation

Why K ka ks kn

a Electron deficiency one

of goes
on
decreasing as

ligand field provides e density for it

bi Inter steric crowding increases

ligand e as

more
ligands surround CMI

DOUBTS
I


Iff

n a lot do n y n o

Far see

WILL

Mb

oxalate forms chelation int 900 not possible by

displacing trans In

which
form ante 180

KLEIN eatin a
A

d Biv
Ip

c X

nii

Colnett Bryce

CEI

Crystal field stablizing Energy

to.GS

auf 1

1 1
Tgif

t o.us

FSE 31 0.410 110.6Ao CASE 4 0.4 Dj t P

FSE O GDo
1.698ft
QQ

Do 20300cm CASE O Y Do

8120 cm I

812 2 97 approx KJ molt

I am 1 107 m z 6 626 10 34 3 108 102 x 0 4102 J mot

mot

I am I 12 5

tide nip

tag
iii eg

46 0.4 Ao t 2 0 6 Do t P

otani

QE

d sp inner orb paramagnetic

arts d3
ggg

n 3

921

Color
logic

916

re Choo n 4 cationic me 4.9 BM

Y anionin

refer o a n't o M o

4
40

Ans is

917 Ans is

915 chose among these 8 species only

Qin
d's Wr I FSE o

tag eg

1 symmetrically filled

d tag g tangy Cest 0

927

lose CFSE cost

ofcomplex becomes less Exothermic

CFSE n more Endothermic

M lablzcz

21

c
c c c

is
M
b
m
l
m
a ca m
a a
m

C b y
a
e

Color paramagnetism often results in colored species

extended n conjugation

polarization effect

d d transitions
f f

CTP charge transfer phenomenon

high energy visible photon absorb

R W

O O B

Y G

lower energy photons transmitted yellow colored species

it
M

do is

d pale colored complex

transition is possible a responsible

maine for color

iit L M transitions

EI

which colored
do rarely d cases

cases are

Mnoy Mno Muzo7 Croy 22052 Hatioy

pink green orange Yellow orange orange

purple

liquid


605 V05 roach

Blue orange red

yyyyg1 orange red vapors

fI

intense colors even when species is diamagnetic

EMPIE

Kaffe Can 6

d d Koz para

Yellow orange orange

K2 Croy CTP NO para

yellow brown

Aggro
ctr fulteroly s d d

red blue

Koz paramagnetism
Mn20y CTP

yellow

orange

Assign these 3 colors to there 3 complexes

M Ho ta Initials talents

blue colored green colored yellow colored

Red photons abs u I photons abs

yellow orange abs

more S F L more D more mom E portion

gap absorbed

lets E portions I

transmitted

Heleptimpleart
Elon

Cr Nhs H2o Ée 42015 no no

SE WEI SE

AA

tangy Liga

Ni 12 PPL

Wrc SEI

tetrahedral
WeÉ Sq planar

Rhd Phs Cotto

4273 F3

Wilkinson's

WFLA

Catalyst In sp'd

ACP

SFC
Glatz

ee

paramagnetic

cn

Edited

it

inner
Cicco

9
Gioia

Entz

folacin


2 T I
I

20 22 6 8 40 t 4 6 2 24 6 23
If I 36 54 36

36

Ii 25 1511512402

1 6 4 1
86