Chemistry of Coordination Compounds - Chapter 19: Color Theory

Page III-19-1 / Chapter Nineteen Lecture Notes
Chemistry of Coordination Color Theory

Compounds - Chapter 19
Where does the color of objects come from?
From the paint covering the object!
Where does the paint gets its color?
From the paint pigments!
What are the pigments?
Chemistry 223
Colorful transition metal compounds!
Professor Michael Russell
MAR MAR
Why Study Transition Metals Periodic Table

¿ Transition metals found in nature
©Rocks and minerals contain transition metals
ôRed rubies (Cr), blue sapphires (Fe and Ti)
d block transition elements
©Many biomolecules contain transition metals
ôVitamin B12 (Co), Hemoglobin, myoglobin, and
cytochrome C (all Fe)
¿ Transition metals used in industry
©Material science (steel, alloys)
©Transition metal compounds are used as pigments f block transition elements
ôTiO2 (white), PbCrO4 (yellow), Fe4[Fe(CN)6]3
(Prussian blue)
MAR MAR
d-Block Transition Elements Transition Metals

VIIIB ¿ General Properties
IIIB IVB VB VIB VIIB IB IIB
©Have typical metallic properties (malleable, etc.)
Sc Ti V Cr Mn Fe Co Ni Cu Zn ©Not as reactive as alkali and alkaline earth metals
©Have high melting points, high boiling points, high
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd density
La Hf Ta W Re Os Ir Pt Au Hg ©Have 1 or 2 s electrons in valence shell
©Differ in # d electrons in n-1 energy level
Most have partially occupied d subshells in ©Exhibit multiple oxidation states
©Both paramagnetic and diamagnetic ions exist
common oxidation states
©Most ions deeply colored (crystal field theory)
MAR MAR

Electronic Configurations Oxidation States of Transition Elements
Element Configuration
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Sc [Ar]3d14s2
+1 +1
Ti [Ar]3d24s2
V [Ar]3d34s2 +2 +2 +2 +2 +2 +2 +2 +2 +2
Cr [Ar]3d54s1 +3 +3 +3 +3 +3 +3 +3 +3 +3
Mn [Ar]3d54s2 +4 +4 +4 +4 +4 +4
Fe [Ar]3d64s2 +5 +5 +5 +5
Ni [Ar]3d84s2 +6 +6 +6
Cu [Ar]3d104s1 +7
Zn [Ar]3d104s2
MAR loss of ns e-s
MAR loss of ns and (n-1)d e-s
Electronic Configurations of Transition Metal Ions Paramagnetism and Diamagnetism

Paramagnetic species have unpaired electrons while
Electronic configuration of Fe ions: diamagnetic species have all paired electrons
Paramagnetic species are attracted or repulsed by
Fe – 2e- → Fe2+ - e- → Fe3+ magnetic fields; the magnitude of the effect depends
[Ar]3d64s2 [Ar]3d6 [Ar]3d5 on the number of unpaired electrons
Examples:
valence ns electrons
Paramagnetic Cr [Ar]
removed first, 3d 4s
then n-1 d electrons
Diamagnetic Pd [Kr]
4d 5s
MAR MAR
Coordination Chemistry Coordination Chemistry

Transition metals act as Lewis acids and form A coordination compound has one or more complexes.
complexes or complex ions with Lewis bases or Examples: [Co(NH3)6]Cl3, [Cu(NH3)4][PtCl4],
ligands
[Pt(NH3)2Cl2]
Fe3+(aq) + 6 CN-(aq) → Fe(CN)63-(aq) The coordination number is the number of donor atoms
Lewis acid Lewis base Complex ion
bonded to the central metal atom or ion in the complex.
Ni2+(aq) + 6 NH3(aq) → Ni(NH3)62+(aq) Example: [Co(NH3)6]3+ coordination number = 6
Lewis acid Lewis base Complex ion
Example: [PtCl4]2- coordination number = 4
Complex contains central metal ion bonded to one or more
molecules or anions Most common = 6, 4 and 2
Coordination number determined by ligands
Lewis acid = metal = center of coordination
Lewis base = ligand = molecules/ions covalently bonded
to metal in complex
MAR MAR

Common Geometries of Complexes Common Geometries of Complexes

Coordination Number Geometry
Coordination Number Geometry
4 tetrahedral
2 (most common)
Examples: [Zn(NH3)4]2+, [FeCl4]-
and
Linear
4 square planar
Example: [Ag(NH3)2]+
(characteristic of metal ions with 8 d e-s)
Example: [Ni(CN)4]2-
MAR MAR
Common Geometries of Complexes Coordination Chemistry

Coordination Number Geometry Charge of complex = sum of charges on the
metal and the ligands
6
Charge of coordination compound = sum of
(most common of all metal charges on metal, ligands, and
coordination numbers) counterbalancing ions
[Fe(CN)6]3- [Co(NH3)6]Cl2
Examples: [Co(CN)6]3-, [Fe(en)3]3+ +2

+3 6(-1) 6(0) 2(-1)
octahedral
anionic complex neutral compound
MAR MAR
Coordination Chemistry Monodentate Ligands

Monodentate ligands possess only one
Ligands - aka Lewis bases accessible donor group.
©classified according to the number of bonds to H2O is a good example since all metal ions exist
central metal
as aqua complexes in water
©"dentate" = "tooth"
Monodentate Ligand Examples:
©Examples
ômonodentate =1 ©H2O, CN-, NH3, NO2-, SCN-, OH-, X- (halides),
chelating agents CO, O2-
ôbidentate=2
ôtetradentate=4 Example Complexes:
ôhexadentate = 6
©[Co(NH3)6]3+
ôpolydentate = 2 or more donor atoms
©[Fe(SCN)6]3-
MAR MAR

Bidentate Ligands Bidentate Ligands

Bidentate Ligands have "two teeth", able to bond oxalate ion ethylenediamine
with metal at two separate places
Bidentate Examples:
© oxalate ion = C2O42- * *
© ethylenediamine (en) = NH2CH2CH2NH2 * *
ortho-phenanthroline
© ortho-phenanthroline (o-phen)
*
Example Complexes:
*
© [Co(en)3]3+ Donor Atoms
© [Cr(C2O4)3]3-
© [Fe(NH3)4(o-phen)]3+
MAR MAR
Bidentate Ligands Bidentate Ligands
Fe(o-phen)32+:
MAR MAR
Bidentate Ligands EDTA

Another bidentate ligand: A commonly used polydentate ligand
Dimethylglyoxime (dmg)
Forms 1:1 complexes with most
metals except Group IA
Ni(dmg)2 (from lab):
Forms stable, water soluble complexes
High formation constants
A primary standard material
See the movie "Blade" (!)
MAR MAR

EDTA O EDTA
H
Six Donor Regions
C
N
M
* *
* *
* *
EDTA (Ethylenediamine tetraacetic acid) will adapt

its coordination number to bond with the metal
MAR MAR
Porphine, an important
Other Chelating Agents
EDTA chelating agent found in
nature
Formation constants (Kf) for some
metal - EDTA complexes.
Ion log K Ion log K Ion log K
Fe3+ 25.1 Pb2+ 18.0 La3+ 15.4 +
Th4+ 23.2 Cd2+ 16.5 Mn2+ 14.0
Cr3+ 23.0 Zn2+ 16.5 Ca2+ 10.7
Bi3+ 22.8 Co2+ 16.3 Mg2+ 8.7
Cu2+ 18.8 Al3+ 16.1 Sr2+ 8.6
Ni2+ 18.6 Ce3+ 16.0 Ba2+ 7.8
MAR MAR
Myoglobin Coordination Environment of Fe2+ in

Oxymyoglobin and Oxyhemoglobin
Myoglobin, an Fe-containing
protein that stores O2 in cells
MAR Oxymyoglobin
MAR

Nomenclature of Coordination Compounds Nomenclature: IUPAC Rules

The cation is named before the anion. When naming a Neutral ligands are referred to by their usual name
complex: with these exceptions:
¿ Cations named first, then anions. Anion metal gets
©water, H2O = aqua
-ate ending
¿ Ligands are named first in alphabetical order. Most ©ammonia, NH3 = ammine
ligands have -o ending; multiple ligands use Greek ©carbon monoxide, CO = carbonyl
prefixes ©hydroxide, OH- = hydroxo
¿ Metal atom/ion is named last with the oxidation state in If the ligand name already contains a Greek prefix, use
Roman numerals. alternate prefixes for multiple occurrences:
¿ Use no spaces in complex name ©bis-, 2; tris-, 3; tetrakis-,4; pentakis-, 5; hexakis-, 6
¿ See Coordination Compounds Handout ©The name of the ligand is placed in parentheses; i.e.
bis(ethylenediamine)
MAR MAR
Nomenclature Nomenclature
Tris(ethylenediamine)nickel(II) ion
Co(H2O)62+ Pt(
Hexaaquacobalt(II) ion
H2O as a ligand is aqua Cu(NH3)42+
Tetraamminecopper(II) ion [Ni(NH2C2H4NH2)3]2+
IrCl(CO)(PPh3)2
Pt(NH3)2Cl2 cis-diamminedichloroplatinum(II)
Vaska’s compound
NH3 as a ligand is ammine Carbonylchlorobis(triphenylphosphine)iridium(I)
Most metals in this section octahedral,
MAR some tetrahedral/square planar (Cu, Pt) MAR
Cisplatin
Nomenclature: IUPAC Rules
cis-[PtCl2(NH3)2]
[CoCl(NH3)5]Cl2
pentaamminechlorocobalt(III) chloride
K2[Cd(CN)4]
Potassium tetracyanocadmate(II)
NiCl2(en)2
square planar Pt(II)
Dichlorobis(ethylenediamine)nickel(II)
coordination number 4
CrCl3(C4H8O)3 (C4H8O = tetrahydrofuran)
cis-isomer
Trichlorotris(tetrahydrofuran)chromium(III)
the first of a series of platinum coordination complex-
based anti-cancer drugs (Platinol-AQ)
MAR MAR

Isomerism Coordination Sphere Isomers

Coordination sphere isomers differ if a ligand is
Isomers are compounds that have the same bonded to the metal in the complex, as opposed to
composition but a different arrangement of atoms in being outside the coordination sphere (ionic
space bonding). Different reactivities!
Important in inorganic and organic chemistry Consider [Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Major Types include: [Co(NH3)5Cl]Br → [Co(NH3)5Cl]+ + Br-
©coordination sphere isomers [Co(NH3)5Br]Cl → [Co(NH3)5Br]+ + Cl-
©linkage isomers With AgNO3:
©geometric isomers (cis, trans, mer, fac) [Co(NH3)5Cl]Br(aq) + AgNO3(aq) →
©stereoisomers [Co(NH3)5Cl]NO3(aq) + AgBr(s)
[Co(NH3)5Br]Cl(aq) + AgNO3(aq) →
[Co(NH3)5Br]NO3(aq) + AgCl(s)
MAR MAR
Linkage isomers differ in which

atom of a ligand is bonded to Linkage Isomers Geometric Isomers
the metal in the complex
Consider [Co(NH3)5(ONO)]2+ Geometric isomers have same types and number
of atoms, but they differ in the spatial
and [Co(NH3)5(NO2)]2+ arrangements of the ligands
Inorganic complexes exhibit cis and trans
isomerism in square planar and octahedral
complexes, as well as mer and fac isomers in
octahedral complexes
Geometric isomers lead to different colors,
a: pentaamminenitrocobalt(III)
melting points, boiling points, reactivities,
(yellow color) solubilities, etc.
b: pentaamminenitritocobalt(III)
(red color)
MAR MAR
Geometric Isomers Geometric Isomers
cis isomer trans isomer cis isomer trans isomer

Pt(NH3)2Cl2 - square planar [Co(H2O)4Cl2]+ - octahedral
MAR MAR

Geometric Isomers Optical Isomers

Optical isomers are isomers that are nonsuperimposable
mirror images
Optical isomers are called chiral (handed) and referred to
as enantiomers
A substance is chiral if it does not have a plane of
symmetry
mer isomer fac isomer
[CrCl3(H2O)3] - octahedral
MAR MAR
Enantiomers Properties of Optical Isomers

Optical isomers or enantiomers possess many
identical properties
Enantiomers have similar solubilities, melting
points, boiling points, colors, chemical
reactivity (with nonchiral reagents)
Enantiomers differ in their interactions with
plane polarized light and other chiral reagents
MAR MAR
Optical Isomers Optical Isomers
polarizing polarizing filter

plane
filter plane polarized polarized optically active sample
light (enantiomer) in solution
light
light unpolarized Dextrorotatory (d) = right rotation

source light
Levorotatory (l) = left rotation
(random vibrations)
Racemic mixture = equal amounts
(vibrates in one plane)
of two enantiomers; no net
rotation rotated polarized
light
MAR MAR

Properties of Optical Isomers Crystal Field Theory

Differences in enantiomer reactivity with other chiral Crystal Field Theory is a model for bonding in
reagents can lead to separation methods transition metal complexes
Example: Accounts for color and magnetism of complexes
d-C4H4O62-(aq) + d,l-[Co(en)3]Cl3(aq) →
quite well
chiral reagent racemic mixture Focuses on d-orbitals of metals. Ligands are
considered to be point negative charges
d-[Co(en)3](d-C4H4O62- )Cl(s) +
solid d enantiomer Assumes ionic bonding (no covalent bonding)
l-[Co(en)3]Cl3(aq) +2Cl-(aq) As in organic chemistry, molecular orbital
theory is better but much more complex
aqueous l enantiomer
Very complex procedures, but important (Ritalin, Thalidomide, etc.)

MAR MAR
d orbitals Crystal Field Theory
Electrostatic attractions between the positive metal

ion and the negative ligands bond them together,
lowering the energy of the whole system
The lone pair e-’s on ligands repulsed by e-’s in
metal d orbitals; this interaction is called the
crystal field
The repulsion influences d orbital energies, but not
all d orbitals influenced the same way
MAR
Notice how
Crystal Field Theory (b) and (c)
exhibit
Octahedral Crystal Field

- direct
overlap
between d
(-) Ligands attracted to (+) - - orbitals and
metal ion; provides ligands
stability +
- -
d orbital e-’s repulsed by
(–) ligands; increases d
-
orbital potential energy
ligands approach along x, y, z axes

MAR d Orbitals and the Ligand Field
Crystal Field Theory Crystal Field Theory
Lobes directed at ligands

Lobes directed between ligands
greater electrostatic repulsion = higher potential energy
less electrostatic repulsion = lower potential energy
Crystal Field Theory

Crystal Field Splitting Energy
octahedral crystal field dz2 dx2- y2
_ _ dz2 dx2- y2
d orbital energy levels
Magnitude of ∆O
_ _ _ ∆o determined by metal ion
and ligand
E
dxy dxz dyz
isolated
gas phase
_____
metal ion metal ion in octahedral
complex dxy dxz dyz
d-orbitals ∆0 = crystal field splitting energy (J, kJ, etc.) in an
MAR (degenerate) MAR
octahedral (o) field
metal ion in octahedral

Octahedral Crystal Field complex
Crystal Field Theory
d orbital energy levels dz2 dx2- y2 Crystal Field Theory can be used to account for
_ _
the colors of complexes as well as magnetic
properties
∆o
A complex must have a partially filled metallic d
_ _ _ subshell to exhibit color; i.e. a complex with
E d0 or d10 is colorless
dxy dxz dyz
isolated Amount of paramagnetism depends on ligands;
gas phase i.e. [FeF6]3- has five unpaired electrons while
_____
metal ion
Metal ion and the nature of the [Fe(CN)6]3- has only one
ligand determines the magnitude
d-orbitals
of ∆o
MAR MAR

Visible Spectrum Visible Spectrum

wavelength, nm
(Each wavelength corresponds to a different color)
400 nm 700 nm
higher energy lower energy
Compounds/complexes with color absorb specific

wavelengths of visible light (400 –700 nm); wavelengths White = all the colors (wavelengths)
not absorbed are transmitted
MAR MAR
More on Colors More on Colors
absorbed
color
observed
color
[Cu(NH3)4]2+:
absorbs yellow, …so observed color of
orange, and red… complex is navy blue.
The color observed in a compound/complex is actually the The color observed in a compound/complex is actually the
complementary color of the color absorbed complementary color of the color absorbed
Colors of Transition Metal Complexes Colors of Transition Metal Complexes

Absorption of UV-visible radiation by compound or
complex occurs only if the radiation has the energy
green light
needed to raise an e- from its ground state (highest white red light
observed
∆ absorbed
occupied orbital or HOMO) to an excited state light
(usually the lowest unoccupied orbital or LUMO)
The light energy absorbed = energy difference For transition metal Absorption raises an
between the ground state and excited state, or complexes, ∆ electron from the lower d
corresponds to subshell to the higher d
E = ELUMO - EHOMO = hν = hc/λmax energies of visible subshell.
light.
MAR MAR

Colors of Transition Metal Complexes Colors of Transition Metal Complexes

The magnitude of depends on the ligand
field (i.e. types of ligands) and the metal, and white red light
green light
determines the color of the complex ∆  observed
light absorbed
Different complexes exhibit different colors due (lower
energy
to the magnitude of light)
larger ∆ = higher energy light absorbed, shorter
wavelengths
smaller ∆ = lower energy light absorbed, longer [Cr(H2O)6]3+
wavelengths
H2O is a "weak field ligand"
MAR MAR
Colors of Transition Metal Complexes Chromium(III) with different ligand fields
white blue light orange light

light ∆ absorbed observed
(higher
energy
light)
[Cr(en)3]3+
en is a "strong field ligand"
MAR MAR
Colors of Transition Metal Complexes Spectrochemical λmax

Series
The Spectrochemical Series:
Examples with chromium(III):
Smallest ∆ Largest ∆
∆ increases Complex λmax (nm)
CrCl63- 736 largest λmax, smallest ∆
I- < Br- < Cl- < OH- < F- < H2O < NH3 < en < O2 < CN- < CO Cr(H2O)63+ 573
Cr(NH3)63+ 462
Cr(CN-)63- 380 smallest λmax, largest ∆
strong field
weak field
I- < Br- < Cl- < OH- < F- < H2O < NH3 < en < O2 < CN- < CO
Smallest ∆ Largest ∆
∆ increases
MAR MAR

Electronic Configurations of Transition Metal
Paramagnetism of Transition Metal Complexes Complexes
Many complexes / compounds are paramagnetic due to Filling electron shells via CH 221:
unpaired d electrons ¿ lowest energy vacant orbitals are occupied first
The degree of paramagnetism dependent on ligands ¿ electrons fill degenerate orbitals singly until no longer
("ligand field") possible (Hund’s rule), then pair (Pauli Exclusion)

Example with Fe3+:
These rules help minimize repulsions between electrons.
[Fe(CN)6]3- has 1 unpaired d electron
These rules work well for gas-phase transition metal ions,
[FeF6]3- has 5 unpaired d electrons but they are not always followed by transition metal
Crystal Field Theory answers this discrepancy complexes in a ligand field
MAR MAR
Electronic Configurations of Transition Metal d-orbital energy level diagrams

Complexes octahedral complex
For complexes in a ligand field, d orbital occupancy
depends on and pairing energy, P d1
¿ Electrons assume the configuration with the lowest
possible energy "cost"
¿ If > P ( large; strong field ligand), e-'s pair up in
lower energy d subshell first, referred to as a low spin
complex
¿ If < P ( small; weak field ligand), e-'s spread out
among all d orbitals before any pair up, referred to as
a high spin complex one unpaired electron
MAR MAR
d-orbital energy level diagrams d-orbital energy level diagrams

octahedral complex octahedral complex
d2 d3
two unpaired electrons three unpaired electrons
MAR MAR


d4 d5
high spin low spin high spin low spin

∆<P ∆>P ∆<P ∆>P
MAR MAR one unpaired electron
four unpaired electrons two unpaired electrons five unpaired electrons

d6 d7
high spin low spin high spin low spin

∆<P ∆>P ∆<P ∆>P
MAR four unpaired electrons no unpaired electrons MAR three unpaired electrons one unpaired electron

d8 d9
two unpaired electrons one unpaired electron
MAR MAR

d-orbital energy level diagrams Electronic Configurations of Transition Metal

octahedral complex Complexes
d10 To determine which d-orbital energy level diagram
to use on a complex or compound:
©determine the oxidation # of the metal
©determine the # of d e-’s
©determine if ligand is weak field or strong field
©draw energy level diagram
no unpaired electrons
diamagnetic
colorless
MAR MAR
Example with Co(NH3)63+ Example with Co(NH3)63+

The absorbance spectrum of 1. What is the name of the complex?
Co(NH3)63+ is shown to the right. Each ammonia is neutral; hence, this is a cobalt(III)
complex
Ammonia is named "ammine"; hence,
Name = hexaamminecobalt(III) ion
1. What is the name of the complex?
2. What is the coordination number? 2. What is the coordination number?
3. How many d electrons does the complex possess?
There are six monodentate ammonia ligands around
4. Will this be a high spin or low spin complex?
the cobalt(III) ion; hence, this is a six coordinate
5. Is the compound paramagnetic? compound, or the coordination number = 6
6. What is the value of ∆ for this complex?
7. What will be the observed color of the complex? What
color is absorbed?
MAR MAR
Example with Co(NH3)63+ Example with Co(NH3)63+

3. How many d electrons does the complex possess? 5. Is the compound paramagnetic?
This is a d6 low spin complex in an octahedral field.
Cobalt(III) ions have the electron configuration:
Three degenerate d orbitals are filled first, followed by
[Ar]3d6 (two 4s and 1 3d electron removed) the remaining two orbitals.
This complex has six d electrons (d6) Since each orbital holds two electrons, the three lower
orbitals are full and the complex is diamagnetic
4. Will this be a high spin or low spin complex?
To answer this, we need to look at the spectrochemical series.
NH3 is considered a strong field ligand, which implies that ∆, the
splitting energy, will be greater than the electron pairing
energy (P).
The octahedral NH3 ligand field makes this a low spin complex
low spin
∆>P
MAR MAR no unpaired electrons
Example with Co(NH3)63+ λmax Example with Co(NH3)63+ λmax
The absorbance spectrum of The absorbance spectrum of

Co(NH3)63+ is shown to the right. Co(NH3)63+ is shown to the right.
7. What will be the observed color of the complex?

6. What is the value of ∆ for this complex? What color is absorbed?
Notice that λmax = 500. nm in the spectrum, and Since λmax is 500. nm in the spectrum, this is the
technically this is a question asking for ∆ since the wavelength that is absorbed.
complex is in an octahedral field
Using 500. nm, the chart to the right implies that
∆O = ∆E = hν = hc/λmax the complex is absorbing the color green
∆O = 6.626∗10−34 J s ∗ 2.998*108 m s-1 / 500.*10-9 m The complementary color is the color that is
∆O = 3.97*10-19 J or actually observed by our eyes. Red is
opposite green, so the observed color should
∆O = 239 kJ/mol be red
MAR MAR
metal ion in
d-orbital energy level diagrams for d-orbital energy level tetrahedral complex
tetrahedral complexes diagram for tetrahedral
complexes dxy
_ d_xz _dyz
∆Τ
_ _
E
isolated dz2 dx2- y2
gas phase
metal ion only high spin;
_____ opposite of
octahedral
d-orbitals
MAR MAR
d-orbital energy level diagrams for d-orbital energy level metal ion in square
square planar complexes diagram for square planar complex
planar complexes __
dx2- y2
__ dxy
__ dz2
E __ __
isolated
gas phase dxz dyz
_metal
_ _ ion
__ only low spin,
d-orbitals more complex
transitions
MAR MAR

Example: Arterial Blood Example: Venous Blood
Strong field
large ∆O Weak field

small ∆O
d6, low spin d6, high spin

Bright red due to Bluish color due to
absorption of greenish light absorption of orange light
MAR MAR
End of Chapter 19
Hostile Elements
See:
✴ Chapter Nineteen Study
Guide
✴Important Equations
(following this slide)
✴End of Chapter Problems
(following this slide)
MAR MAR
End of Chapter Problems: Test Yourself

Important Equations, Constants, and Handouts
from this Chapter:
1. Give the electron configuration for the Cr3+ ion. Is it paramagnetic or

• The primary focus of this diamagnetic?
2. Which of the following ligands is expected to be monodentate and
chapter is to introduce you to which might be polydentate? a. CH3NH2 b. CH3CN c. en d. Br-1
coordination compound e. phen
nomenclature (with a little 3. Give the oxidation number of the metal ion in [Mn(NH3)6]SO4
review of metals, electron 4. Give the oxidation number of the metal ion in Cr(en)2Cl2
configurations, etc. as well 5. Write the formula for potassium tetrachloroplatinate(II)
6. Write the formula for tetraamminediaquairon(II)
from CH 221 and CH 222) 7. Name the following: [Ni(C2O4)2(H2O)2]2-
8. Name the following: Pt(NH3)2(C2O4)
Handouts:
• Coordination Compounds Handout

End of Chapter Problems: Answers
1. [Ar]3d3, paramagnetic
2. a, b, d: monodentate c, e: polydentate (bidentate)
3. +2
4. +2
5. K2[PtCl4]
6. [Fe(NH3)4(H2O)2]2+
7. diaquabis(oxalato)nickelate(II) ion
8. diammineoxalatoplatinum(II)

Chemistry of Coordination Compounds - Chapter 19: Color Theory

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Chemistry of Coordination Compounds - Chapter 19: Color Theory

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Page III-19-1 / Chapter Nineteen Lecture Notes

Chemistry of Coordination Color Theory

From the paint covering the object!

Where does the paint gets its color?

From the paint pigments!

What are the pigments?

Why Study Transition Metals Periodic Table

d-Block Transition Elements Transition Metals

Page III-19-1 / Chapter Nineteen Lecture Notes

Electronic Configurations Oxidation States of Transition Elements

Electronic Configurations of Transition Metal Ions Paramagnetism and Diamagnetism

Coordination Chemistry Coordination Chemistry

Page III-19-2 / Chapter Nineteen Lecture Notes

Common Geometries of Complexes Common Geometries of Complexes

Common Geometries of Complexes Coordination Chemistry

Examples: [Co(CN)6]3-, [Fe(en)3]3+ +2

Coordination Chemistry Monodentate Ligands

Page III-19-3 / Chapter Nineteen Lecture Notes

Bidentate Ligands Bidentate Ligands

Bidentate Ligands Bidentate Ligands

Bidentate Ligands EDTA

Page III-19-4 / Chapter Nineteen Lecture Notes

EDTA (Ethylenediamine tetraacetic acid) will adapt

Myoglobin Coordination Environment of Fe2+ in

Page III-19-5 / Chapter Nineteen Lecture Notes

Nomenclature of Coordination Compounds Nomenclature: IUPAC Rules

Page III-19-6 / Chapter Nineteen Lecture Notes

Isomerism Coordination Sphere Isomers

Linkage isomers differ in which

Geometric Isomers Geometric Isomers

cis isomer trans isomer cis isomer trans isomer

Page III-19-7 / Chapter Nineteen Lecture Notes

Geometric Isomers Optical Isomers

mer isomer fac isomer

Enantiomers Properties of Optical Isomers

Optical Isomers Optical Isomers

polarizing polarizing filter

light unpolarized Dextrorotatory (d) = right rotation

Page III-19-8 / Chapter Nineteen Lecture Notes

Properties of Optical Isomers Crystal Field Theory

Very complex procedures, but important (Ritalin, Thalidomide, etc.)

d orbitals Crystal Field Theory

Electrostatic attractions between the positive metal

Octahedral Crystal Field

ligands approach along x, y, z axes

Crystal Field Theory Crystal Field Theory

Lobes directed at ligands

Crystal Field Theory

metal ion in octahedral

Page III-19-10 / Chapter Nineteen Lecture Notes

Visible Spectrum Visible Spectrum

Compounds/complexes with color absorb specific

More on Colors More on Colors

Colors of Transition Metal Complexes Colors of Transition Metal Complexes

Page III-19-11 / Chapter Nineteen Lecture Notes

Colors of Transition Metal Complexes Colors of Transition Metal Complexes

Colors of Transition Metal Complexes Chromium(III) with different ligand fields

white blue light orange light

Colors of Transition Metal Complexes Spectrochemical λmax

Page III-19-12 / Chapter Nineteen Lecture Notes

("ligand field") possible (Hund’s rule), then pair (Pauli Exclusion)

Electronic Configurations of Transition Metal d-orbital energy level diagrams

d-orbital energy level diagrams d-orbital energy level diagrams