COORDINATION
COMPOUNDS
SIMPLY CONCISE
isomerism theories
basics &
nomenclature
COORDINATION COMPOUNDS
SALTS
SIMPLY CONCISE
simple salts addition salts
compounds in which the double salts complex salts
metal atoms are bound
[Link]₂ .6H₂O K₄[Fe(CN)₆]
to a number of molecules
by sharing of electrons K⁺ + Cl⁻ + Mg²⁺ 4K⁺ + [Fe(CN)₆]⁴⁻
SOME IMPORTANT TERMS
coordination entity
counter K₄[Fe(CN)₆]
ion
SIMPLY CONCISE ligands
central metal
atom/ion
Coordination Number:
number of ligand donor atoms to which the metal is directly bonded
CN = no. of σ bonds between CMA and ligands
LIGANDS
The ions or molecules bound to the central atom/ion
Types of Ligands:
1) monodentate - can bind to metal ion through a single donor atom
eg: Cl⁻, Br⁻, NO₂⁺, NH₃, H₂O, CH₃-NH₂
SIMPLY CONCISE
2) bidentate - can bind to metal ion through two donor atoms
eg: H₂N-CH₂-CH₂-NH₂, C₂O₄²⁻
3) polydentatedentate - can bind to metal ion through more than
one donor atoms. eg: edta⁴⁻, N(CH₂CH₂NH₂)₃
4) ambidentate - two diff. donor atoms but only one can donate at a
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
SIMPLY CONCISE
IUPAC NAMING
Formula Writing:
1) cation first followed by anion
2) for complex part, CMA first followed by ligands in alpha order
3) charge on cation = charge on anion
SIMPLY CONCISE
pentaamminenitro-N-cobalt(III) chloride
+3 0 -1
[Co(NH₃)₅(NO₂)]Cl₂
tetraamminenickel(II) tetrachloridonickelate(II)
+2 0 +2 -4
[Ni(NH₃)] [NiCl₄]
IUPAC NAMING
Name Writing:
1) cation first followed by anion
2) for complex part, ligands first in alpha order followed by CMA
3) balance the charge and mention the OS of CMA
SIMPLY CONCISE
4) for multiple ligands - di, tri, tetra or bis, tris, tetrakis
5) if complex ion is anion, name of metal ends with -ate
+4 +2 -6
K₄[Fe(CN)₆] potassium hexacyanoferrate(II)
+2 +2 -4 0
(NH₄)₂[Ni(C₂O₄)₂(H₂O)₂] ammonium diaquabis(oxalato)nickelate(II)
and
+1 0 +1 -2 for both complexed be same
opp
[Ag(NH₃)₂][Ag(CN)₂] diamminesilver(I) dicyanoargentate(I)
~ > In case of the complexed not charge should
,
COORDINATION
COMPOUNDS
isomerism theories
basics &
nomenclature
ISOMERISM
same formula - diff. arrangements
Structural
SIMPLY CONCISE
Isomerism Isomerism
Stereo
same formula same formula
diff. bonds same bonds
diff. arrangements
STRUCTURAL ISOMERISM
1) Ionization 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(NH₃)₅Br]SO₄ [Co(NH₃)₅Br]²⁺ + SO₄²⁻
SIMPLY CONCISE
[Co(NH₃)₅SO₄]Br [Co(NH₃)₅SO₄]⁺ + 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(H₂O)₆]Cl₃ & [Cr(H₂O)₅Cl]Cl₂.H₂O
~
Here
,
water is
present as free solvent
STRUCTURAL ISOMERISM
3) Linkage Isomerism - arises in a coordination compound
containing ambidentate ligand.
[Co(NH₃)₅NO₂]Cl₂ & [Co(NH₃)₅ONO]Cl₂
SIMPLY CONCISE
4) Coordination isomerism - arises from the interchange of ligands
between cationic and anionic entities of different metal ions
present in a complex.
[Co(NH₃)₆][Cr(CN)₆] & [Cr(NH₃)₆][Co(CN)₆]
STEREOISOMERISM
1) Geometric Isomerism - arises in heteroleptic complexes due to
different possible geometric arrangements of the ligands.
CN - 2 & 3 => No GI
CN - 4 -> tetrahedral => No GI Las all four bonds are equivalent)
SIMPLY CONCISE
S For CN = M )
square planar => various cases
Ma₄ => No GI (four same sigunes)
Assymmetrical
bidentate
Ma₃b => No GI 13 same ligands) ↑ ligands
Ma₂b₂ => 2 GIs Mabcd => 3 GIs call d
3 iff
.) M(ab)₂ => 2 GIs
a b b a a b a b a d a a a b
M M M M M M M
a b a b d c c d c b b b b a
cis trans trans cis cis cis trans
cis isomers
(named wrt a & c) go trans isomes s
.
STEREOISOMERISM
1) Geometric Isomerism - arises in heteroleptic complexes due to
different possible geometric arrangements of the ligands.
CN - 6 => various cases
Ma₆ => No GI
Ma₅b => No GI
Ma₄b₂ => 2 GIs SIMPLY CONCISE
Ma₄bc => 2 GIs Ma₃b₃ => 2 GIs
b a b a b a
a a a b a a a b b a a b
M M M M M M
a a a b a a a c a a a b
b a c a b b
trans cis trans cis mer fac
octahedral octahedral
Ma₂b₂c₂ => 5 GIs Mabcdef => 15 GIs at meridian at same
face
STEREOISOMERISM
2) Optical isomerism - isomers that exists as non superimposable
mirror images of each other.
b b no sym. a a plane of sym.
SIMPLY CONCISE
2 OI same
M M M M
a b b a a b b a
a a a a
dextro laevo
a a no sym. b b plane of sym.
a a a a b a a b
2 OI same
M M M M
a a a a a a a a
a a b b
dextro laevo
ANSWER IN COMMENT
Q1) Which of the following has optical isomers:
a) [Co(H₂O)₄(en)]³⁺ b) [Co(en)₂(NH₃)₂]³⁺
c) [Co(NH₃)₃Cl]⁺ d) [Co((en)NH₃)₂]²⁺
SIMPLY CONCISE
Q2) These two are : identical / GI / OI
a en
a
en M en M
a
a en
COORDINATION
COMPOUNDS
Valence Bond Werner’s Crystal Field
Thory Theory Theory
WERNER’S THEORY
Valencies
primary valency secondary valency
SIMPLY CONCISE
ionisable non ionisable
non directional directional
satisfied by satisfied by
anions ligands
OS of the metal CN of the metal
[Cr(H₂O)₆]Cl₃
VALENCE BOND THEORY
1) metal - ligand bond arises when a filled ligand orbital overlaps a
vacant hybrid orbital of metal.
2) central metal atom provides requisite no. of vacant orbitals of
same energy, for that they hybridize their (n-1)d, ns, np, nd orbitals.
CN SIMPLY CONCISE
hybridisation geometry 3) strong field ligands like NH3,
CN-, CO force pairing of electrons.
4 sp³ tetrahedral
4 dsp² sq. planar
5 sp³d tri. bipyramidal
outer orbital complex
6 sp³d² octahedral or high spin complex
inner orbital complex
6 d²sp³ octahedral
or low spin complex
VALENCE BOND THEORY
+3
strong
~
ligand +3
[Co(NH₃)₆]³⁺ [Cr(NH₃)₆]³⁺
Co : 4s²3d⁷ 6 monodentate Cr : 4s¹3d⁵
Co⁺³ : 4s⁰3d⁶ Ligunds Cr⁺³ : 4s⁰3d³
3d 〜
4s 4p
SIMPLY CONCISE 3d 4s 4p
d²sp³ (inner d) d²sp³ (inner d)
octahedral no pairingnt
low spin complex
usedintiD
Exybridisation as
is low in unpaired
octahedral
not possiblehigh spin complex
Energy
diamagnetic CNO unpaired If condition paramagnetic
'
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
- same Energy
>
3) in an isolated gaseous metal atom, the d orbitals are degenerate,
.
SIMPLY CONCISE
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.
strong ligands produces strong forces
but does not explain reh
Hybridisation why
strong and weak
ligands underga pairing
Also , does not explain Quantative interpretation of
magnetic behaviour
CRYSTAL FIELD THEORY
Experiences more repulsion
a) splitting of d orbitals in octahedral field: so its
energy increases
-directed towards(ligands)
axis
eg
dz² dx²-y²
along
zethey
axis
are
Shigner
SIMPLY CONCISE
}
3/5Δₒ
Energy
barycentre orbitas
Δₒ
2/5Δₒ
[
t₂g
field
dxy dyz dzx
crystal bet axis less
repulsion
splitting Sθ less
energy
CRYSTAL FIELD THEORY
a) splitting of d orbitals in tetrahedral field:
actachedral
θ
ligands directedNetE Δₜ = 4/9 Δₒ
the axis so
Stetrahedral
splitting
gets invertech dxy dyz dzx
SIMPLY CONCISE t₂
}
barycentre 2/5Δₜ
Δₜ
s.
3/5Δₜ
e
dz² dx²-y²
CFSE(OCt > CFSELtet)
as it contains only ligands
CRYSTAL FIELD THEORY
Factors affecting CFSE:
1) Oxidation state of metal
OS CFSE
2) nature of metal
SIMPLY CONCISE
3d > 4d > 5d
3) number of ligands
no. of ligands CFSE
4) nature of ligands
I⁻ Br⁻ SCN⁻ Cl⁻ S²⁻ F⁻ OH⁻ ox²⁻
H₂O NSC⁻ edta⁴⁻ NH₃ en CN⁻ CO
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
CFSE <
pairing Energy)
eg
(CFSE) pairing energy
eg
SIMPLY CONCISE
d³ d³
t₂g t₂g
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
Of
a) Δₒ P
eg
do Enters b) Δₒ P
eg
SIMPLY CONCISE
d⁴ d⁴
t₂g t₂g
14Enters
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d⁵ csume) d⁵ csume)
for both) t₂g
for both
t₂g
10
5
d
. … .
5 … 10
d
.
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d⁶ d⁶
t₂g t₂g
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d⁷ d⁷
t₂g t₂g
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d⁸ d⁸
t₂g t₂g
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d⁹ d⁹
t₂g t₂g
CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P
eg eg
SIMPLY CONCISE
d¹ᵒ d¹ᵒ
t₂g t₂g
In tctrahedral CISE is not that much so
Note
ー possibility
of much
_
pairing is less
JAHN TELLER DISTORTIONS
distortions in octahedral geometry which decreases sym. & energy
Reason: unsymmetric filling of eg and t2g orbitals
a JTD is absent in symmetric
a a octahedral field
SIMPLY CONCISE
M
half filed d³, d⁵ (WFL)
a a
full filed d⁶ (SFL) , d¹ᵒ
a
a both d⁸
a
a a a a
M M
a a a a
a
a
when extra eg e⁻ when extra eg e⁻
is in dz² orbital is in dx²-y² orbital
BONDING IN METAL CARBONYLS
CO CO CO CO
CO CO
OC
Ni Fe CO OC Mn Mn CO
OC CO OC OC OC
CO CO CO CO
SIMPLY CONCISE
O
CO CO
OC C CO
OC CO
OC Co Co CO Co Co
OC CO
OC C CO
CO CO
O
BONDING IN METAL CARBONYLS
metal-carbon bond in metal carbonyls possess both σ and π character.
Π Π Π* M - C σ bond : donation of lp of
carbonyl C to the vacant d orbital
M - C π bond : donation of e⁻ pair
SIMPLY CONCISE
σ O
M C from a filled d orbitals of M into the
vacant antibonding orbital of CO
Π
Synergic Bonding
M - C bond strengthens
C - O bond weakens
charge density on metal
IMPORTANCE OF COORDINATION COMPOUNDS
1) significance in biological systems:
a) chlorophyll - complex of Mg
b) haemoglobin - complex of Fe
c) vitamin B12 - complex of Co
SIMPLY CONCISE
2) significance in medicinal chemistry:
a) cis platin - anti cancer agent
b) edta - lead poisoning
3) extraction processes of metals like silver and gold
4) wilkinson catalyst - hydrogenation of alkene