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H2N NH2
N N
dien
H
N N NH2 NH2
bipy H2N NH2 H2N
S tren
NH2 PR2
R = Ph, diphos
en R = Me, dmpe NH2
HN N N
NH2 PR2
trien O- -
O
SCH3
O HN NH2
- acac salen
SCH3
O H H
N N
O O-
- EDTA
C O2C CO2-
ox N N N N
C - -
O O O2C CO2- H H
cyclam
Transition metal complex (coordination
compound) terminology
• Coordination number - number of ligands coordinated to a metal ion,
2-12.
• Coordination geometry or stereochemistry (octahedral, tetrahedral,
square planar) - geometrical arrangements of ligands (donor groups)
about a metal ion.
Examples of coordination complexes
PPh3 PPh3
Cl PEt3
Ni Ni Ni
Br PPh3 Cl PPh3 Et3P Cl
Br Cl
Comparison of space filling models of
triphenylphosphine, P(C6H5)3 = PPh3, and
triethylphosphine, P(CH2CH3)3 = PEt3
Space filling models depict Van der Waals radii for atoms and reflect
the effect volume that they occupy
Effect of coordination number and geometry
on absorption spectrum
H2N
OH2 2+ H2N 2+ H2 3+
H2
H2O OH2 N NH2 N NH2
Ni Ni Co
H2O OH2 N NH2 N NH2
OH2 H2 H N H2 H N
2
2
Effect of ligand on absorption
spectra (and color)
Formulas/structures of some Pt(II) complexes
PtCl2·4NH3 3 [Pt(NH3)4]Cl2
PtCl2·3NH3 2 [Pt(NH3)3Cl]Cl
PtCl2·2NH3 0 cis-[Pt(NH3)2Cl2]
trans-[Pt(NH3)2Cl2]
PtCl2·NH3·KCl 2 K[Pt(NH3)Cl3]
PtCl2·2KCl 3 K2[PtCl4]
Transition metal complex (coordination
compound) terminology
• Isomers
– Constitutional (structural) isomer - one of two or more
compounds having the same composition but differing in their
atom connectivities.
– Stereoisomer - one of two or more compounds having the same
atom connectivities but different spatial arrangements of atoms.
• Diastereoisomer – stereoisomers not related by mirror
images
• Enantiomer - one of a pair of species that are non-
superimposable mirror images.
Types of Isomerism
Constitutional
Stereo
(structural)
Diastereomers
Linkage
(geometric)
Enantiomers
Ionization
(optical)
Hydration
X L X
M cis
M L X
L
X
L
L X
M trans
X L
PPh3 PPh3
Cl PEt3
Ni Ni Ni
Br PPh3 Cl PPh3 Et3P Cl
Br Cl
Stereoisomers: Diastereoisomers
L L
L X
ML4X2 L
M
X
M
L X cis
L X
L L
X X
L L L L
M M trans
L L L L
X X
L L
L X L X
M M trans
X L X L
L L
Examples of coordination complexes
H2N 1+ Cl H2N
H2 H2 1+ H2 3+
Cl NH2 N N N NH2
Co Co Co
Cl NH2 N NH2
N N H2 H N
H2N H2 Cl H2 2
Stereoisomers: Diastereoisomers
ML3X3 X X
L L L L
M M mer
L X L X
X X
X X
L X L X
M M fac
L X L X
L L
Stereoisomers: Enantiomers (optical isomers)
F F
Br C C Br
Cl Cl
H H
Optical rotation
Stereoisomers: Enantiomers
Rotate by 180E
F F
Br C C Br
Cl Cl
H H
Stereoisomers: Enantiomers
H2N
H2 3+
N NH2
Co
N NH2
H2 H N
2
Stereoisomers: Enantiomers
H
H2N NH2 N N
dien = = = N N
NH
NH2 H2N
How many stereoisomers (diastereoisomers and enantiomeric forms)
can exist for [Co(H2NCH2CH2O)3]?
The tetradentate ligand shown below forms six-coordinate complexes
with Co(III) having the composition [CoLX2]+ where X is a mondentate
ligand. How many diastereoisomers can be formed?
HN NH2 N N
=
HN NH2 N N
Energy changes for formation of ML6n+
n+ n+ n+
M +6L ML6 ML 6
(octahedral)
E
d z 2 d x2 - y 2
)E
e-e replusion d xz dxy dyz
differential replusions
of d orbitals
electrostatic
attraction
Magnetic properties depend upon the
magnitude of Δo
I– < Br– < SCN– < Cl– < NO2– < F– < OH– < C2O42– ≈ H2O < NCS–
< py < NH3 < en < bipy < phen < NO2– < PR3 < CN– ≈ H– < CO
Weak Field Strong Field
Small Δ Large Δ
Frequently high spin Frequently low spin
Poor σ Donors Strong σ Donors
π Bases (donors) π Acids (acceptors)
Constructing an energy level diagram for a
complex with F donor ligands
F*
np F*
ns eg *
F*
)
t2g
(n-1) d n
L orbitals
F
y z z F
F
x x y
x
Energy level diagram for complex
with F donor ligands
F*
np
F*
ns eg*
F*
)
t2g
(n-1) d n
L orbitals
F
F
F
Metal-ligand B-bonding interactions
F*
np
F*
ns eg* t2g
y z z
F*
x x y ) t
2g
B*
x (n-1) d
n L orbitals
B
F
F
F
HOMO and LUMO for cyanide ion
E p
s
Energy level diagram for complex
with F and B acceptor ligands
F*
np
F*
B*
n L pi acceptor
ns eg* orbitals
F*
)
(n-1) d t2g
B
L orbitals
F
F
F
Energy level diagrams for complexes with F
only, F plus B donor, and F plus B acceptor
ligands
np
L pi acceptor
ns orbitals
)
)
)
(n-1) d
L orbitals
Effect of B-donor and B-acceptor interactions
on ) in octahedral complexes
2.04
Ti
2.02 Mn(III),Fe(III) are h.s.
2.00 V Mn Fe Co(III) is l.s.
M-O distance/Ǻ
1.98
1.96
Cr
1.94
1.92
1.90
1.88
Co
1.86
0 1 2 3 4 5 6 7
No. of d electrons
[Mn(OH2)6]2+
Electronic absorption spectra
Ph
Base
Ph
N N
N N
Ph Zn Ph + Base Ph Zn Ph
N N N N
Ph
Ph
• d1 and d9, and high-spin d4 and d6 ions have only one spin-
allowed transition; high-spin d2, d3, d7 and d8 have three spin-
allowed transitions
Transitions in d1 and d2 complexes
dx2-y2 dz2
I– < Br– < SCN– < Cl– < NO2– < F– < OH– < C2O42– ≈ H2O < NCS–
< py < NH3 < en < bipy < phen < NO2– < PR3 < CN– ≈ H– < CO
Weak Field Strong Field
Poor σ Donors Strong σ Donors
π Bases (donors) π Acids (acceptors)
Variation of )O in octahedral Ti(III) complexes
Ti(III) is a d1 ion and exhibits one absorption in the electronic
spectrum of its metal complexes due to transition of the electron
from the t2g (lower energy) orbitals to the eg (higher energy)
orbitals. The energy of the absorption corresponds to )O.
Ligand )O/cm-1*
Br- 11,400
Cl- 13,000
(H2N)2C=O 17,550
NCS- 18,400
F- 18,900
H 2O 20,100
CN- 22,300
*E = h< = hc/8
Factors affecting the magnitude of ) (Crystal
Field Splitting)
● Geometry and coordination number. For similar ligands )t
will be about 4/9 )O. This is a result of the reduced number of
ligands and their orientation relative to the d orbitals. Recall that
the energy ordering of the orbitals is reversed in tetrahedral
complexes relative to that in the octahedral case.
Thermodynamic vs kinetic stability
ΔG‡
M–X + Y
ΔGº
M–Y + X
The nature of the M–X and M–Y bonding interactions determine ΔGº and
ΔG‡.
•ΔGº is a function of the relative strengths of M–X vs. M–Y.
•ΔG‡ is a function of the lability of the M–X bond.
[Cu(NH ) 2+ ]
[Cu(OH2)4]2+ + 4 NH3 W [Cu(NH3)4]2+ + 4 H2O β = 34
4 [Cu2+ ][NH ]4
3
Speciation is determined by ligand concentration
[Cu(OH2)4]2+ + n NH3 = [Cu(OH2)4-n(NH3)n]2+
1.0
0.9
0.8
n=0 n=4
0.7
0.6
Fraction
n=1 n=3
n=2
0.5
0.4
0.3
0.2
0.1
0.0
6 4 2 0
-log[NH3]
Chelating ligands have larger formation constants
than comparable non-chelating ligands; the Chelate
Effect is largely (substantially?) entropic in origin