V.

SANTHANAM
DEPARTMENT OF CHEMISTRY
SCSVMV
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 e- in partially filled d sublevel absorbs visible light
 moves to slightly higher energy d orbital

Magnetic properties due to unpaired electrons

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 Consist of a complex ion and necessary counter ions
[Co(NH3)5Cl]Cl2

 Complex ion: [Co(NH3)5Cl]2+

Co3+ + 5 NH3 + Cl-
1(3+) + 5 (0) + 1(1-)
2+

 Counter ions: 2 Cl-

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 Transition metals act as Lewis acids
 Form complexes/complex ions
Fe3+(aq) + 6CN-(aq)  Fe(CN)63-(aq)

Lewis acid Lewis base Complex

Ni2+(aq) + 6NH3(aq)  Ni(NH
ion 3)62+(aq)

Lewis acid Lewis base Complex

ion

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 Complexcontains central metal ion
bonded to one or more molecules or
anions
 Lewisacid = metal = center of
coordination
 Lewisbase = ligand = molecules/ions
covalently bonded to metal in
complex
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 [Co(NH3)6]Cl3 [Pt(NH3)4]Br2

Complex ion remains intact upon dissolution in water

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 Species where transition metal ion is
surrounded by a certain number of ligands.

 Transition metal ion: Lewis acid

 Ligands: Lewis
bases

 Co(NH3)63+

 Pt(NH3)3Br+

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 Molecule or ion having a lone electron pair
that can be used to form a bond to a metal
ion
 (Lewis base).
 coordinate covalent bond: metal-ligand
bond

 monodentate: one bond to metal ion

 bidentate: two bond to metal ion
 polydentate: more than two bonds
to a metal ion
possible
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 1. Cation then anion
 2. Total charges must balance to zero
 3. Complex ion in brackets

 K2[Co(NH3)2Cl4]

 [Co(NH3)4Cl2]Cl

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 1. Cation then anion
 2. Ligands
 in alphabetical order before metal
ion
 neutral: molecule name*
 anionic: -ide  -o
 prefix indicates number of each
 3. Oxidation state of metal ion in () only if
more than one possible
 4. If complex ion = anion, metal ending  -ate

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 K2[Co(NH3)2Cl4]

potassium
diamminetetrachlorocobaltate(II)

 [Co(NH3)4Cl2]Cl

tetraamminedichlorocobalt(III) chloride

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20_441

Isomers
(same formula but different properties)

Structural Stereoisomers
isomers (same bonds, different
(different bonds) spatial arrangements)

Geometric
Coordination Linkage Optical
(cis-trans)
isomerism isomerism isomerism
isomerism

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 Coordinationisomerism
 Composition of the complex ion varies.

 [Cr(NH3)5SO4]Br
 and [Cr(NH3)5Br]SO4

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 Ligand isomerism:
 Same complex ion structure but point of
attachment of at least one of the ligands differs.

 [Co(NH3)4(NO2)Cl]Cl
 and [Co(NH3)4(ONO)Cl]Cl

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[Co(NH3)5(NO2)]Cl2 [Co(NH3)5(ONO)]Cl2
Pentaamminenitrocobalt(III) Pentaamminenitritocobalt(III)
chloride chloride

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 Geometric isomerism (cis-trans):

 Atoms or groups arranged differently

spatially relative to metal ion

[Pt(NH3)2Cl2]

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20_444
Cl
Cl
H3N NH 3
H3N NH3
Co Co

H3N NH 3 H3N Cl

Cl NH 3

Cl Cl

Co Co
Cl

Cl
(a) (b)
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  Optical isomerism:
20_446

 Have opposite effects on plane-polarized light

 (no superimposable mirror images)

Polarizing
filter

Tube
containing
Unpolarized
sample
light 
Polarized
light

Rotated
polarized light
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20_448

Mirror image
of right hand
Left hand
Right hand

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20_449

N N
Mirror image
Co
N N of Isomer I

N
N N

N N N N
Co Co
N N N N
Isomer I Isomer II
N N

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20_450

Cl The trans isomer and Cl Isomer II cannot be

its mirror image are superimposed exactly
N N identical. They are not N N on isomer I. They are
Co isomers of each other. Co not identical structures.
N N N Cl
Cl Cl Cl
Cl N
N N N Cl N N
trans Co cis Co Co
N N N N N Cl

Cl Isomer I N Isomer II N

Isomer II has the same

structure as the mirror
(a) (b) image of isomer I.

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 Models for the bonding in transition
metal complexes must be consistent with
observed behavior.

 Specific data used include stability (or

formation) constants, magnetic
susceptibility, and the electronic (UV/Vis)
spectra of the complexes.

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Werner’s Theory
Sidgwick’s Theory
Crystal Field Theory
Ligand Field Theory

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 Valence Bond theory provides the
hybridization for octahedral complexes.

 For the first row transition metals, the

hybridization can be: d2sp3 (using the 3d, 4s
and 4p orbitals), or sp3d2 (using the 4s, 4p
and 4d orbitals).
.

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 Thevalence bond approach isn’t used
because it fails to explain the electronic
spectra and magnetic moments of most
complexes

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