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Figure 19.1
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Figure 12.27
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4p
Unpaired
Electrons
Element
4s
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
1
2
3
Oxidation States
See Table 19.2 for common oxidation states of the
1st-row transition metals
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Sc
Ti
V
Mn
Cr
Zn
Fe
Co
Ni
Cu
-2.08 V
-1.63 V
-1.2 V
-1.18 V
-0.91 V
-0.76 V
-0.44 V
-0.28 V
-0.23 V
0.34 V
reducing ability
Sc3+ + 3eTi2+ + 2eV2+ + 2eMn2+ + 2eCr2+ + 2eZn2+ + 2eFe2+ + 2eCo2+ + 2eNi2+ + 2eCu2+ + 2e-
See Table 19.3 (opposite signs b/c reduction vs. oxidation potentials)
Oxidation Potentials
Mn+ + ne-
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Transition-metal complexes
are extremely colorful.
Color is influenced by:
metal ion (dn configuration),
oxidation state, and
coordinated ligands.
K3[Fe(CN)6]
[Co(NH3)5Cl]Cl2
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Oxidation States of Mn
2 MnO4-(aq) + 5 H2C2O4(aq) + 6 H+(aq)
2 Mn2+(aq) + 10 CO2(g) + 8 H2O(l)
V2+(aq)
+3
V3+(aq)
+4
VO2+(aq)
+5
VO2+(aq)
V0(s)
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HVO42-
VO(H2O)52+
V(H2O)63+
V(H2O)62+
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HVO42-
VO(H2O)52+
V(H2O)62+
V(H2O)63+
2 V(H2O)63+(aq) + 4 H2O(l)
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d6
d7
d8
d9
d0
d0
d0
d10
No d electrons no color.
Full d orbitals no color.
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[Ni(en)(H2O)4]2+ [Ni(en)2(H2O)2]2+
green/blue
blue
[Ni(en)3]2+
purple
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MO Theory - Part I
The d orbitals reach only a very
short distance from the
nucleus they are essentially
non-bonding orbitals
MO Theory Part II
The movement of electrons between
these levels is the source of the
chemical properties of transition
metal complexes (color, magnetic
properties, reactivity).
n
ground state
excited state
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Coordination Compounds
The real bulk of inorganic chemistry occurs in the
reactions of coordination compounds (or complexes).
A coordination compound contains a complex ion and
counter ion
Complex ion: a central metal ion surround by one or
more ligands
Counter ion: ion that balances the charge of a
complex ion to form a neutral compound
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Fig 19.6
Cu+
2, 4
Mn2+
4, 6
Sc3+
Ag+
Fe2+
Au+
2, 4
Cr3+
Co2+
4, 6
Co3+
Ni2+
4, 6
Au3+
Cu2+
4, 6
Zn2+
4, 6
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acid
base
[Co(OH2)6]2+
base
acid
base
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acid
2 Fbase
Coordination Chemistry
Since metal cations can acts as Lewis acids, and ligands have
electron pairs to donateinorganic coordination compounds
are often formed by Lewis acid / base chemistry
d-block elements:
oxidation state
Mn+
M
ne
Mn+ + 6 Lqacid base
[Mn+L6](n-6q)
metal complex
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Coordination compounds
What are some aspects of coordination compounds we
should understand?
Coordination number
Ligands
Isomers and chirality
Coordination Number
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Ligands
Ligands can bond in one or more sites on the metal ion:
1 (monodentate): NH3, CO, H2O, I, Cl, etc.
2 (bidentate): acac, bpy, en, dppe
3 (tridentate): dien
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HOOC
H2
C
HOOC
H2
C
CH2
H2C
C
H2
COOH
C
H2
COOH
H2
C
H2 C
N
Mn+
n = 2 to 4
H2 C
C
H2
O
O
O
CH2
H2 C
O
N Fe
1
CN
CN
NH
vs.
H
N Fe
OH2
OH2
OH2
CN
[Fe(TACN)(CN)3]
2+
[Fe(TACN)(H2O)3]2+
unreactive
reactive
yellow
blue
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NH
H
N Fe
NH
CN
CN
N Fe
OH2
OH2
OH2
CN
2+
-1 (-3) = +2
+2 (0) = +2
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cis chlorides
trans chlorides
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Isomers (Preview)
2 or more chemical species with identical
composition but different properties
Naming
Coordination
Compounds
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4. Use prefixes (mono-, di-, tri-, tetra-, penta- and hexa-) for the
number of simple ligands; (bis-, tris-, tetrakis-, etc. for multiple
complex ligands)
5. Metal oxidation state is denoted with roman numerals in
parentheses.
6. Ligands are named in alphabetical order
7. If the complex ion has a negative charge, add ate to the
metal name (vanadate, ferrate, etc.). Sometimes the Latin
name is used.
Naming Examples
[Co(NH3)5Cl]Cl2
pentaamminechlorocobalt(III) chloride
K3Fe(CN)6
potassium hexacyanoferrate(III)
[Fe(en)2(NO2)2]2SO4
bis(ethylenediammine)dinitroiron(III) sulfate
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Metal Ion
(electron acceptor)
Unoccupied hybrid orbital
Ligand
(electron donor with a lone pair)
Mn+
Figs. 19.20
and 19.19
Hybridization (L.E.M.)
Linear: sp
Ag(CN)2-
Ni(CN)42-
Tetrahedral: sp3
CoCl42-
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Octahedral Complexes
Co(NH3)63+
Fig 19.21
dxy
d z2
d x2-y2
dyz
dxz
Close
overlap,
higher
energy
d
t2g (dxy, dyz, dxz)
The nature of
the ligands
affects this
difference
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Example:
Co3+ (3d6)
eg orbitals
eg orbitals
t2g orbitals
t2g orbitals
Weak Field
Strong Field
t2g orbitals
Strong Field
eg orbitals
t2g orbitals
Example:
Co3+ (3d6)
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Spectrochemical series
CN- > NO2- > en > NH3 > H2O > OH- > F- > Cl- > Br- > IStrong-field
ligands
Large
small
Weak-field
ligands
eg orbitals
Strong Field
t2g orbitals
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Examples
Examples
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Examples
Examples
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eg orbitals
t2g orbitals
t2g orbitals
photon absorption
Absorbed Wavelength
Yellow
Red
Violet
Blue
Green
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Appears
dz2 dx2-y2
absorbs
green
increasing energy
dxy
dyz
dxz
G B I V
dz2 dx2-y2
absorbs
blue
hn
dxy
dyz
dxz
dz2 dx2-y2
absorbs
violet
hn
dxy
dyz
dxz
Tetrahedral Complexes
None of d-orbitals point
directly AT the ligands
R O Y
hn
dxy
dxz
dz2
Fig 19.27
dyz
tet
dx2-y2
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Example:
2-
Cl
Co
Cl
Cl
Cl
Energy
dxz
dz2
dyz
tet
dx2-y2
Fig 19.29
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is influenced by:
The Mn+ oxidation state
(M3+) > (M2+) > (M+)
Example,
=
Fe(II)(NH3)62+
12,800 cm-1
vs.
Fe(III)(NH3)63+
26,000 cm-1
is influenced by:
The identity of the ligands
Example,
[Fe(II)L6]2+
L=
=
H2 O
8,900
CN
30,000
Cl
5,900 cm-1
Spectrochemical series
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[Ni(en)(H2O)4]2+
[Ni(en)2(H2O)2]2+
[Ni(en)3]2+
Appears:
green
green/blue
blue
purple
Absorbs:
red
red / orange
orange
yellow
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[Cr(OH2)6]2+
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High-spin
Examples:
[Cr(OH2)6]2+
Low-spin
[Cr(CN)6]4-
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Demo: Ammines
Cu(H2O)42+(aq) + 4 NH3(aq) Cu(NH3)42+(aq) +
4 H2O(l)
Spectator Ion: SO42
19.4 Isomerism
19.5 Bonding in complex ions: The localized electron model
19.6 The crystal field model
19.7 The molecular orbital model
19.8 The biological importance of coordination complexes
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Classes of isomers
Fig 19.9
Coordination Isomers:
[Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4
SO4
Br
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Fig 19.10
Linkage Isomers:
NO2- can bond to the
metal through one of the
oxygens or through the
nitrogen
yellow
red
[Co(NH3)5(NO2)]Cl2
Pentaamminenitrocobalt(III)
chloride
[Co(NH3)5(ONO)]Cl2
Pentaamminenitritocobalt(III)
chloride
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Stereoisomers:
3
Cis
Geometrical isomers
Cis = together
Trans
Fig 19.11
Chloride ligands
Cis
Trans
green
violet
Fig 19.12
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Optical Isomers
Figure 19.15
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Figure 19.16
Isomers I and II
for [Co(en)3]3+
Nonsuperimposable
mirror images!
[Co(en)2Cl2
Trans isomer
Achiral Complex
]+
Cis isomer
Chiral Complex
Fig 19.17
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Achiral Complex
Chiral Complex
(I and III are enantiomers)
C
C
*
O
D-Alanine (unnatural)
C
*
O
C
O
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BIOINORGANIC CHEMISTRY
TMs serve as the active site within many large biological
molecules.
Key is ability of TM metals to
Coordinate with and release ligands
Easily undergo oxidation and reduction
Human body contains only 0.01% TM by mass, divided
among 3d Cr, Mn, Fe, Co, Ni, Cu, Zn and 4d Mo. Nature has
used the most abundant TMs:
3d abundance >> 4d/5d.
Fe is most abundant 3d element and the most used
biologically.
Mo is the most abundant 4d/5d element.
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BIOINORGANIC CHEMISTRY
Functions of these trace metals:
Electron Carriers. TM have >1 stable oxidation state.
Oxidized form can pick up electrons; reduced form can
release electrons elsewhere as pH or other conditions
change.
Oxygen Carriers. TM have >1 stable CN. At different O2
partial pressures, can bind or release this metabolically
crucial small molecule.
Hemoglobin Molecule
Figures 19.33,19.36
Heme
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