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Coordination Compounds
2.
3.
Chem 17
UP Diliman
Institute of Chemistry
4.
6.
7.
8.
9.
10.
11.
12.
13.
References for the Images and Examples Used for this Lecture PPT:
a. Petrucci, General Chemistry 2010
b. Whitten, General Chemistry 2011
Two
coordination compounds
[CoCl(NH3)5]Cl2.
[Co(NH3)6]Cl3
Coordination Compounds
Important terms
Nomenclature
Structures
Isomerism in Coordination Compounds
Structural (Constitutional) Isomers
Stereoisomers (Geometric, Optical Isomerism)
Bonding in Coordination Compounds
Electronic Configuration of Metal Cations and Hybrid
Orbitals Concept
Crystal Field Theory
Color and the Spectrochemical Series
Kinetics of Ligand Exchange
Electrochemistry of Complexes
Other Applications
.
H3N . + BF3
.
H3N . BF3
Ag 2 NH 3 [ Ag ( NH 3 ) 2 ]
4
2-
aq
2
Cu(OH) 2 s 4 NH3aq Cu(NH 3 ) 4 aq 2 OHaq
Co(NH ) 2 2 OH
Co(OH) 6 NH
2 s
3 aq
3 6
aq
aq
Ion/
Molecule
Name
Name as a
Ligand
NH3
ammonia
ammine
CO
carbon monoxide
carbonyl
Cl-
chloride
chloro*
Ion/Molecule
Name
Name as a
Ligand
CN-
cyanide
cyano
CO3-2
carbonate
carbonato
OHS2SO42SCN-
hydroxide
sulfide
sulfate
thiocynate
hydroxo
sulfido
sulfato
Thiocynato-S
Thiocynato-N
Ion/Molecule
CO
NO
Name
Carbon dioxide
Nitrogen
monoxide
NO2-
nitrite
ONOPH3
nitrito
phosphine
Name as a
Ligand
10
Carbonyl
Nitrosyl
Nitro
Nitrito-N
Nitrito-O
Phosphine
(en) = ethylenediamine
is an example of a
bidentate ligand
11
12
Petrucci
ox
Co2+
ox
Co(ox)2 2
A square planar
complex
13
14
You do it!
15
16
1.
2.
You do it!
3.
4.
18
4.
Examples:
[Fe(en)3]+3 is Tris(ethylenediamine)iron(III) cation.
[Co(ox)(en)2]+1 is Bis(ethylenediamine)oxalatocobaltate(III) anion
19
ClS2O2OHCNNO3SO42-
chloro
sulfido
oxo
hydroxo
cyano
nitrato
sulfato
[PdClBr(OH)2(en)] is Bromochloroethylenediaminedihydroxopalladium(IV)
complex, a neutral ligand.
20
5.
6.
NH3
H2O
CO
NO
CS
7.
ammine
aqua
carbonyl
nitrosyl
thiocarbonyl
Others:
[Pt(OH2)2CO(en)NO] is Diaquacarbonylethylenediaminenitrosylplatinum(IV)
complex, a neutral ligand.
21
22
[Ni(NH3)4(OH2)2](NO3)2
tetraamminediaquanickel(II) nitrate
23
24
Fluoro
Chloro
Bromo
Iodo
Azido
Cyano
Thiocyanato
FClBrIN3CN*SCN-
Now: Thiocynato-S
Hydroxo
Ammine
Methylamine
OHNH3
H3CNH2
Phosphine (phosphane)
Pyridine
Common
Aqua
H 20
Carbonyl
CO
Thiocarbonyl
CS
Nitrosyl
NO
Nitro (or Nitrito-N) NO2Nitrito-O
ONO(O-bonded)
Nitrato
NO3Amido
NH2Sulfato
SO4-2
25
Chelating Ligands
27
PR3
py
Sodium tetrahydroxozincate(II)
Dichlorobis(ethylenediammine)cobalt(III) Nitrate
Triaquabromoplatinum(II) Chloride
Potassium trioxalatochromate(III)
Sodium pentacyanomanganate(IV)
Ammonium
diamminetetraisothiocyanochromate(III)
Tetraamminedinitroplatinum(IV) bromide
Hexammineruthenium(III) tetrachloronickelate(II)
Trans-diamminedinitroplatinum(II)
Tri-aqua-cis-dibromochlorochromium(III)
28
Coordination Chemistry
Molecular Geometries
Isomerism in Complexes
30
Petrucci
Coordinati
on Number
Geometry
Metal Hybridization
Example
linear
sp
Ag[NH3)2]+
tetrahedral
sp3
[Zn(CN)4]2-
square planar
dsp2 or sp2d
[Ni(CN)4]2-
trigonal bipyramid
dsp3
[CuCl 5 ]-3
Fe(CO)5
Square pyramidal
d2sp2
octahedral
d2sp3 or sp3d2
[Ni(CN)5]3-
[Co(en)3]+3
[Fe(CN)6]431
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Isomers:
Structural
(constitutional)
Stereoisomerism
(configurational)
Structural isomers:
Differ in basic structure.
1. Ionization
2. Hydrate
3. Linkage
4. Coordination
Stereoisomers:
Same number and type of ligands with the same
mode of attachment, but differ in the way the
ligands occupy space around the metal ion.
1. Geometric
a. Cis-trans
b. Fac-mer
2. Optical
-has mirror image
which are not
superimposable
34
1. Structural*** isomerism:
2.1 Diastereomers
** Conformational isomers (identical
bonding but have different bends or twists)
**
Geometric isomers
Example: Cis vs. Trans isomers
Fac vs. Mer isomers
35
36
[Pt(NH3)4Cl2]Br2
H3 N
H3 N
Cl
Pt
+2
2-
N H3
Cl
[Pt(NH3)4Br2]Cl2
H3 N
N H3
H3 N
Counter ions
are Br-.
Br
Pt+4
Br
N H3
+2
2-
N H3
For example:
.
[Fe(OH2)4Cl2]Cl2 2H2O
Counter ions
are Cl-.
37
[Cr(OH2)6]Cl3
OH2
H2 O
H2 O
Cr
OH2
[Cr(OH2)5Cl]Cl2. H2O
3+
OH
OH
Counter ions
are 3 Cl-.
OH2
H2 O
H2 O
Cr
OH2
38
[Cr(OH2)5Cl]Cl2. H2O
[Cr(OH2)6]Cl3
2H2O
2+
OH2
Cl
H2 O
H2 O
OH
OH2
OH
Counter ions
are 3 Cl-.
Counter ions
are 2 Cl- and
1 water.
Cr
3+
OH
39
OH2
H2 O
H2 O
Cr
OH2
[Cr(OH2)4Cl2]Cl2.
2+
Cl
OH
Counter ions
are 2 Cl- and
1 water.
OH2
H2 O
H2 O
Cr
OH2
1+
Cl
Cl
Counter ions
are 1 Cl- and
2 waters.
40
10
[Co(NH3)5ONO]Cl2
Pt
4 -
Cl
4 +
N H3
Cl
N H3
Cl
Pt
Cl
[Pt(NH3)4][PtCl6]
Cl
H3 N
Cl
H3 N
Cl
Pt
Cl
Nitrito -O
2 -
2 +
N H3
Cl
N H3
Cl
Cl
Pt
H3 N
H3 N
Cl
[Pt(NH3)4Cl2][PtCl4]
N H3
Nitrito-N
2+
N H3
Co O
[Co(NH3)5NO2]Cl2
H3 N
N
O
H3 N
N H3
Co N
N H3
2+
O
O
Note which atom in the ligand is bound to the central metal atom.
Another example: SCN- ligand can bind either through S or N.
42
Ionization
Isomerism
[CrSO4(NH3)5]Cl
pentaaminesulfatochromium(III) chloride
[CrCl(NH3)5]SO4
pentaaminchlorochromium(III) sulfate
Coordination Isomerism
Nitrite ion
Linkage
[Co(NH3)6][CrCN6]
hexaaminecobalt(III) hexacyanochromate(III)
isomerism illustrated
[Cr(NH3)6][CoCN6]
The nitrite ion can bind through the nitrogen lone pair or the oxygen lone pair.
(a) Pentaamminenitrito-N-cobalt(III) cation.
(b) Pentaamminenitrito-O-cobalt(III) cation.
hexaaminechromium(III) hexacyanocobaltate(III)
11
[Co(H2O)5Cl]Br2
[CuCl4(NO2)]3-
[Cr(CH3NH2)4Cl2]Br
45
46
H3N
H3N
Cl
Pt
Cl
H3N
Cl
Cl
Pt
N H3
12
FIGURE 24-5
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50
(NH
F 3)`
(NH3)`
F
(NHF
3)`
F
(NH3)`
F
Se
F
F3)`
(NH
FIGURE 24-6
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F
Se
F
(NH
F 3)`
octahedral
Meridional
octahedral
Facial
52
13
The geometric
isomers of
[Ma3b3c3]n complex
trans-diammine-trans-diaqua-trans-dichlorocobalt(III) ion
[CoCl3(NH3)3],
A [Ma3b3]n type of
complex
Geometric isomers
N H3
Cl
H2O
Co
Cl
O
N H H2
All trans
54
Geometric isomers
trans-diammine-cis-diaqua-cis-dichlorocobalt(III) ion
N H3
Cl
H2O
Co
O
H2
Cl
NH3
N H3
Cl
Co
H2O
Cl
NH3
H2O
Cis H2O
Cis Cl
Trans NH3
55
56
14
Geometric isomers
Geometric isomers
cis-diammine-cis-diaqua-trans-
cis-diammine-trans-diaqua-cis-
dichlorocobalt(III) ions
dichlorocobalt(III) ions
Cl
NH3 H O Cl NH3
2
Co
Co
O
H2
N H3 H2O
N H3
Cl
Cl
H2O
OH2
Cl
Cl
Cis NH3
NH3
Co
NH
O H2 3
Cl
Cl
Cis Cl
Trans Cl
OH2
NH3
Co
NH
O H2 3
Trans H2O
Cis NH3
Cis H2O
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L (left)
D (right)
15
Square Planar
complex with 4
different ligands
(e.g.
[PtBrClF(OH)]2-
When the
mirror image
is flipped
sideways, it
becomes
identical to
the original
image
61
62
63
64
16
65
66
A1
A2
Stereoisomer 1
Mirror Image of
Stereoisomer A1
2. 2
If you rotate A2 (along horizontal plane), and then invert along the
z-axis, the resulting structure will be superimposable to A1.
Theres a horizontal plane of symmetry which reflects the bottom
half to the upper half.
67
68
17
Stereoisomer 1
1. /2 twice
A4
A3
Mirror Image of
Stereoisomer A3
Stereoisomer 2
A6
Stereoisomer
Mirror Image of
Stereoisomer A5
70
Formula
# Stereoisomers
Pairs of enantiomers
Ma6
Ma5 b1
Ma4 b2
Ma3 b3
Ma4 bc
***Ma3 bcd
Ma2 bcde
15
Mabcdef
30
15
***Ma2b2c2
Ma2b2cd
***Ma3b2c
0
72
18
bonding in a complex to be an
[Cr(en)(NH3)2(OH2)2]+3
Consider
en
[Cr(en)2(H2O)Cl]+2
73
dxy
Imagine a potential head-on collision of the electrons from the ligands with the
d-electrons of the metal. The octahedral field would not affect directly the xy, yz
and xz lobes.
Canada Inc.
dyz
dxz
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Canada Inc.
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19
eg
t2g
Petrucci
d orbitals
before splitting
d orbitals under
an octahedral field
Canada Inc.
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78
26
1s
Large 0
Strong field ligands
Fe
26
2
2
2s 2 p
3s 2 3 p 6
CN- , CO > NO2- > en > py NH3 > EDTA4- > SCN- > H2O >
ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > ISmall 0
Weak field ligands
4s
d6
3d
Fe 2
1s 2
2s 2 2 p 6
3s 2 3 p 6
4s
26
d6
3d
Fe 3
1s 2
2s 2 2 p 6
3s 2 3 p 6
4s 0
d5
3d
80
20
27
Co
1s
27
2
2
2s 2 p
3s 2 3 p 6
4s
Co 2
28
1s 2
d7
2s 2 p
3d
4s
2s 2 p
4s
4s
d6
3d
29
1s 2
2
2s 2 p
3s 2 3 p 6
1
4s
d10
3d
Instead of
4s2d9
2s 2 p
3s 2 3 p 6
3s 2 3 p 6
d10
3s 2 3 p 6
3d
28
Ni 4
1s 2
d6
2s 2 2 p 6
3d
3s 2 3 p 6
0
82
d5
3d
4s 0
3d
4s 0
29
d8
2s 2 2 p 6
Fe 3
2s 2 2 p 6
1s 2
1s 2
4s
81
Cu 1
Ni 2
4s
26
Cu
3d
1s 2
29
d8
3s 2 3 p 6
28
2
2
3d
3s 2 3 p 6
1s
d7
Ni
Very large O
Cu 2
1s 2
2s 2 2 p 6
3s 2 3 p 6
d9
Small O
[FeCl6]3-
[Fe(en)3]3+
3d
4s 0
83
84
21
27
Co 3
1s 2
2
2s 2 p
3s 2 3 p 6
E
N
E
R
G
Y
d6
3d
4s 0
27
Co 2
1s
2
2
2s 2 p
3s 3 p
4s 0
3d
d7
[CoCl4]2-
eg
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t2g
Most destabilized
t2g
e
g
[Co(NH3)4 ]2+
Least destabilized
87
88
22
FIGURE 24-14
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(f) The energy difference between the dxy and dx2-y2 orbitals in a squareplanar complex is the same as in an octahedral complex because these
orbitals are equally affected by ligand repulsions in both complexes.
90
28
d8
Ni 2
1s 2
d-orbital
splitting
under a
square
planar CF
2s 2 2 p 6
2
Ni
NO2
NO2
3s 3 p
[ Ni( X )4 ]n
3d
4s 0
e
g
If d8 and paramagnetic
t2g versus
[ Ni(ox)( NO2 )2 ]
91
Tetrahedral
Square Planar
92
23
If d6 and magnetic
[ Fe A3 B3 ] property is given
eg
versus
t
II
[ PtAx By ]n
2g
e
g
t
If tetrahedral, the
complex is also
paramagnetic
2g
versus
93
hc
94
Primary colors:
red
green
blue
Secondary colors:
Complementary colors:
Shorter
wavelength,
;
Higher
Frequency,
Higher Energy
Longer
wavelength, ;
Smaller Frequency,
Lower Energy
24
orange
red
yellow
The mixing of
colors
indigo
[CoCl4]-
[Co(NH3)6]2+
green
indigo
The secondary colorsyellow (Y), cyan (C), and magenta (M)are produced in
regions where two of the beams overlap. The overlap of all three beams produces
white light (W).
blue
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red
orange
yellow
indigo
indigo
green
blue
Red-shift
Cl is a weaker field
strength ligand than H2O
Blue-shift
NH3 is a stronger
field ligand than H2O
25
[[Zn(NH3)4]2+]
= 4.1108
[Zn2+][NH3]4
oran
ge
blu
e
yell
ow
gre
en
Effect of ligands on
24-18 of
the FIGURE
colors
coordination
compounds
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1.0 M
-x
____
+x
2.5 M
+ 4x
26
Fast[Cu(H O) ]2+ + 4 NH
[Cu(NH3)4]2+ + 4 H2O
Fast
[CuCl4]2-
[Cu(H2O)4]2
[Cu(NH3)4]2+
[Cu(H2O)4]2+
+4
Cl-
[Cu(Cl)4]2-
+ 4 H2O
When a small amount of water is added, the mixture of [Cu(H2O)4]2+ and [CuCl4]2ions produces a yellow-green color.
When CuSO4 is dissolved in water, a light blue solution of [Cu(H2O)4]2+ forms.
FIGURE 24-20
NH3 molecules readily displace H2O molecules as ligands and produce deep blue
[Cu(NH3)4]2+ (extreme right).
General Chemistry: Chapter 24
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trans-CrCl2(H2O)4+.
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27
Co3+(aq) + e- Co2+(aq)
4
Co3+(aq)
+ 2 H2O(l) 4
Co2+(aq)
Co3+(aq) + e- Co
E = +1.82 V
+4
H+
+ O2(g)
Ecell = +0.59 V
E = +1.82 V
But:
and
Co3+ + 3e-
[Co(NH3)6]3+(aq)
e-
[Co(NH3)6]2+(aq)
E = +0.10 V
E = ?
G formation H TS
Negative
Exothermic
Bond formation
Negative S
Gdissociation H TS
[Co(en)3]3+ or [Co(NH3)6]3+
Explain based on H;S,G, Kf or Kd and E.
G = -zFE =
[Co(en)3
]3+ +
11
1
Positive
Endothermic
Bond Breaking
Positive S
Chelated complex
has smaller
negative Sf
Favored if more
ligands will be
dissociated
28
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Tetrasodium EDTA
FIGURE 24-25
Structure of
Chlorophyll-A
Hemoglobin carries
O2 through the Febonded to the heme.
29
30