COORDINATION

COMPOUNDS

eories
 COORDINATION COMPOUNDS
SALTS

simple salts tT Tey bt

bead taped th which the CO Cy TLL complex salts

ep t oT chat aah ee ola
to a number of molecules (einai bleed K.[Fe(CN)<]
by sharing of electrons K* + Cl- + Mg* rer [Fe(CN).]*
 SOME IMPORTANT TERMS
coordination entity
——_—

counter <— K,[Fe(CN),]

i noo
Tah mL
atom/ion

Coordination Number:
a a eh eC ee ie ah a re
CN = no. of o bonds between CMA and ligands
 LIGANDS
The ions or molecules bound to the central EU ACle
Types of Ligands:
1) monodentate - can bind to metal ion through a single donor atom
eg: CI-, Br-, NO2*, NH3, H20, CH3-NH2
Pam leel-ahceh tweet ie hile mM imme mae Ci lmh clue
eg. H,»N-CH.-CH,-NH,, C,0,7-

3) polydentatedentate - can bind to metal ion through more than

one donor atoms. eg: edta‘*-, N([Link],NH;);
4) ambidentate - two diff. donor atoms but only one can donate ata
time. eg: NO2- & ONO-, SCN- & NCS-

chelation - When a di or polydentate ligand uses its two or more

donor atoms simultaneously to bind the metal ion, it forms a ring
 LIGANDS
COORDINATION COMPOUNDS

neutral ligands
rhe aqua ae ethane-1,2-diamine
NH; ammine od Pea lar
co rela Lolaba CH:-CH:-NH; diethy!
A . let
NO OTe Sa Xo parent
da triphenyiphosphine CH,-CH,-NH,
CH;NH, Gal sdab Amt)

anionic ligands
x- LT Ke NO;- nitrato V t
a i hydrido co;?- carbonato Prete
OH- hydroxo/hydroxido $O;?- sulphito
; (0 Pies ered ato [o) Lore hydrogen sulphito
ns (oot superoxido $O,2- sulphato
ol ea esidababa C,0,?- Ce ateLS
NH imido ; H,N-CH;COO- glycinato
i PLOP ae hydrogen peroxido CH,-C=N-O Pet
CN- cyano/cyanido Pater eet Pray Ie tt LG)
N?- nitrido
Pe azido Rll Fae
N-CH,-CH2-N
Pee cyanato- 0 A ; ; ;
rome oled i rae hie OOC-CH, Sata saa eRe
“3 NO,- Pitta ae Tent] DCE
aml hat ee ade oat)

2 ONO- nitrito - 0
a
¢ SCN" thiocyanato - $
5 ncS- thiocyanato - N

cationic ligands ORR:

fs : Feet
NO: nitrosonium KS Rahs
NO,* ybeaedalit laa i ee
N>H;° Acta eaa) PY UR
ae

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 IUPAC NAMING
Formula Writing:
Phim mclCl Xm aclitele
2) for complex part, CMA first followed by ligands in alpha order
3) charge on cation = charge on anion

pentaamminenitro-N-cobalt(IIl) chloride
+3 0 a

[Co(NH;);(NO2)]Cl,

tetraamminenickel(Il) tetrachloridonickelate(II)
4 O +2 -4

[Ni(NH3;)] [NiCI,]
 IUPAC NAMING
Name Writing:
Phim mclCl Xm aclitele
2) for complex part, ligands first in alpha order followed by CMA
3) balance the charge and mention the OS of CMA
4) for multiple ligands - di, tri, tetra or bis, tris, tetrakis
CDM imetdanl (> aim emeh lime mol mite litem ait Mere ht

+4 +2 -6

K,[Fe(CN);] potassium hexacyanoferrate(II)

+2 +2 mee 0
(NH,)2[Ni(C.0,).(H20)2] ammonium diaquabis(oxalato)nickelate(II)
- fr bolt Compkren> Se LO
[Ag(NH;)2][Ag(CN)2] diamminesilver(!) dicyanoargentate(1)
nominee ee KAW TERY MC BEE
oe TTY Lea
COORDINATION
COMPOUNDS

eories
ISOMERISM

on
 STRUCTURAL ISOMERISM
1) lonization Isomerism - arises when the counter ion in a complex
salt is itself a potential ligand and can displace a ligand which can
then become the counter ion.
[Co(NH;);Br]SO, ==> [Co(NH;);Br]2* + $O,2-
[Co(NH;);SO,]Br ==> [Co(NH;);SO,|* + Br-

2) Hydration Isomerism - isomers differ by whether or not a water

molecule is directly bonded to the metal ion or merely present as
free solvent molecules.
[Cr(H.0),]Cl; & [Cr(H,0),CI]CI,.H,O
Tees Co, ae ak Aros Ree
 STRUCTURAL ISOMERISM
3) Linkage Isomerism - arises in a coordination compound
containing ambidentate ligand.
[Co(NH;);NO,]Cl, & [Co(NH;);ONO|CI,

eorLorel hime eee lemme lle hilet-molmlts (hilek

between cationic and anionic entities of different metal ions
present in a complex.
[Co(NH;)«][Cr(CN)«] & [Cr(NH;).][Co(CN).]

aoe
Ob 10)

eee

a
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 STEREOISOMERISM
1) Geometric lsomerism - arises in heteroleptic complexes due to
different possible geometric arrangements of the ligands.
CN-2&3 => NoGIi -s
=> No era,
- 4 -> tetrahedral
CN all Neneh Wonds ane enpivol 7

Ae eee various cases

me di T D Assy Ard Zan A
Ma,=>N oG i ( Jou, So bdenlate
Ma;b => No GI (3 Sam ens mele
Ma.b, => 2 Gis Mabcd => 3 Gis (atl 3 Ce M(ab), => 2 Gis
a b b a a b a b a d
N74 Ne N74 Ne Ne ’ 3 ox
AY AY AY AY AY
A _— mA _— A _— A _ A _—
cis trans trans cis cis trans
; nels an
(named wrt a & c)
180° trang
— 'sOmod
 STEREOISOMERISM
1) Geometric lsomerism - arises in heteroleptic complexes due to
different possible geometric arrangements of the ligands.

CN - 6 => various cases

Ma, => No Gli
Ma-;b => No Gl
Ma,b, => 2 Gis Ma,bc => 2 Gis Ma;b; =>» 2 Gis
/e) re
re 4 a a vid /e) a sly a a ied |e)

a > a | 7 me ar ai
> 7" - > am | - ae aoa ni -

/e) re ros a
trans cis trans cis

Ma.,b.c, => 5 Gis Mabcdef => 15 Gis

 STEREOISOMERISM
2) Optical isomerism - isomers that exists as non superimposable
mirror images of each other.

b no sym. a plane of sym.

|» a ey
a1
|» peren
yA a
OX:

laevo

a. are S Zab 1 r plane of sym.

os ' rae “201 ©
Vie
En ee

ru
ae an n
— me gp g
a: b
laevo
 ANSWER IN COMMENT
Q1) Which of the following has optical isomers:
a) [Co(H,0),(en)
]* b) [Co(en)2(NHs)2]**
c) [Co(NH;);Cl]* d) [Co((en)NHs3)2]?*

Q2) These two are: identical / GI / Ol

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 COORDINATION
COMPOUNDS

Te Lyle
arn
VT dit cS Crystal Field
Thory ites ie
 WERNER’S THEORY
ETT Ter

primary valency a Ce A Ca
ionisable non ionisable
non directional directional
satisfied by satisfied by
anions ligands
OS of the metal CN of the metal

[Cr(H,0),]Cl;
 VALENCE BOND THEORY
1) metal - ligand bond arises when a filled ligand orbital overlaps a
vacant hybrid orbital of metal.
Pay -Vibtael Manl-axol ohm lahat -Ma-te Lit ei Mel ack lille dice] CMe),
same energy, for that they hybridize their (n-1)d, ns, np, nd orbitals.

CN | hybridisation Cea 3) strong field ligands like NH3,

eer CN-, CO force pairing of electrons.

sq. planar

tri. bipyramidal
outer orbital complex
octahedral —? or high spin complex
> inner orbital complex
d?sp* octahedral :
or low spin complex
 VALENCE BOND THEORY
Stntvy Cre
i ae
[Co(NH:),]** [Cr(NH:;),]**

Co:4s73d’ ¢ monddetate Cr: 4s'3d°

Cot?: 4s°3d° EAS Cr+?: 4s°3d?
er.) ar x a}
DoGERIe H
Pee (inner d) me na ree (inner d)
octahedral w? (ak Laat ad A eh octahedral
low spin complex ste rn ng pean Gat pasibchigh spin complex
diamagnetic (jy PNTeat I eae paramagnetic
ee

colourless colourled
 CRYSTAL FIELD THEORY
1) metal - ligand bond is purely ionic and arises from electrostatic
interactions between the metal ion and the ligand.
2) anionic ligands -> point -ve charge neutral ligands -> dipoles
3)
.in an
.isolated gaseous metal atom, the d
;
orbitals
—* ame Enenig
are degenerate,
and the degeneracy is maintained in a spherically symmetric field
4) the degeneracy of the d orbitals splits in ligand field and the
pattern of splitting depends upon the nature of the crystal field.
nS aL Leg ond aclaeeti Hrhdvg fore
a Se Lege te IL Bw mY mPNC31, av) OD) Oh R10
Strong anh — weak (yard — undorgd “Pairing cece
— Also hee OY SMO TUTS OLN cg a LLL Of ieee
Ea eet (ae) Yih) he Tem
 CRYSTAL FIELD Lt heditel
TUN Cm ama Tun
a) splitting of d orbitals in octahedral field: So ik etal A inc Cah0g )
TES BT mentee Nv VX mY)
ae Z y Rar cm is

3/50.

barycentre CUTTS Rats a

 CRYSTAL FIELD THEORY
a) splitting of d orbitals in tetrahedral field: fi eae
e nse Rita’ Ge ae a LN
Ss bee, splitting
eas inverted dxy dyz dzx
LF

barycentre sa,

miata
3 Avie

i
dz? dx?-y’
ees) > a(S

> ad it combeurng AY 4 de
 CRYSTAL FIELD THEORY
Factors affecting CFSE:
1) Oxidation state of metal
OS < CFSE
2) nature of metal
3d > 4d > 5d
CPM alll ol-laolmite later
no. of ligands «< CFSE
Pehla mom ie hale
I- < Br- K SCN- CK CI- K< S2- K F- K OH- K ox?-
H.O < NSC- < edta‘*- < NH; Cen < CN- < CO
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
Gn alles ae (CFSE > aeaaley | ae
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:

.ee
 d<°v (4 d>°v(p
Loe U Ce PhoM om ol-PEVI CCE MUM LUCE L-JE-M Com LOE
AGZOAHL A1dld IVLSAGD
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) A.<P oe
 JAHN TELLER DISTORTIONS
distortions in octahedral geometry which decreases sym. & energy
Reason: unsymmetric filling of eg and t2g orbitals

te) JTD is absent in symmetric

aw | Ta octahedral field
- a.
M es « half filed —— d°, d° (wrt)
| full filed amr d°(srt), ro aed

re | oXeh aa — ad?
a
| a a
ea ee
- a - a we
| a | a Ofe-io

os fe
iF e A Cm)
a

when
"
extra eg e- when extra eg e- i ere
is in dz? orbital is in dx?-y? orbital OPass
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BONDING IN METAL CARBONYLS
co co Ls
v oc | wy wy
y nn _re—_co oc—Mn Mn—co
oc” | ‘co le ae ae
co rove co co

fe

oc—Co
oc
www ll co
of Pole —_—
ccf ro
Co—cCo
Pee
0

a 4 a Ta | ~¢o
BONDING IN METAL CARBONYLS
metal-carbon bond in metal carbonyls possess both o and m character.

M- Co bond: donation of Ip of
carbonyl C to the vacant d orbital
M - C m bond: donation of e- pair
from a filled d orbitals of M into the
vacant antibonding orbital of CO

Synergic Bonding
M - C bond strengthens
C - O bond weakens

G e charge density on metal

IMPORTANCE OF COORDINATION COMPOUNDS
PR llhicr tt Mle dCs: [cri ee
a) chlorophyll - complex of Mg
b) haemoglobin - complex of Fe
eat xelial iim :1 Peet daal )(-> aol mere
2) significance in medicinal chemistry:
a) cis platin - anti cancer agent
b) edta - lead poisoning
CORD adalat Clem ete Ce mCi eM CaN Cima me tle

OT dex amok NAT em clate (ithe mel <lil- pea

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