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Chapter 20

Transition Metals and


Coordination Chemistry

COORDINATION COMPOUNDS
-- Lewis Acid - Base reactions:
Base electron pair donor
Acid - electron pair acceptor
-- Coordinate covalent bonds
-- ligands, Lewis bases
-- Complex ions called Metal Complexes

ALFRED WERNERS
COORDINATION THEORY
-- Oxidation number of central atom
-- Coordination number
-- Coordination sphere (containing metal ion)
- anions
- cations
- neutral
-- Geometry
- look at hybridization shapes

Formulas and Name of Some Common Ligands


Formula
H2O
NH3
CO
NO
H2NC2H4NH2
OHO2FClBrICN-NCS-SCNSO42SO32NO3-NO -

Name
aqua
ammine
carbonyl
nitrosyl
ethylenediamine
hydroxo
oxo
fluoro
chloro
bromo
iodo
cyano
isothiocyanato*
thiocyanato*
sulfato
sulfito
nitrato*
nitro*

Various
coordination
geometries

Nomenclature of Coordination Compounds

1.The cation is named first in ionic compounds, then the anion.


2.Nonionic compounds are given a one-word name.
3.The following rules pertain to the names of ligands.
a. The ligands are named first and the central atom last.
b. Ligands are named in alphabetical order by their root name.
c. Neutral ligands are named the same as the molecule, except for a few such as
H2O (aqua) and NH3 (ammine), which have special names.
d. Anionic ligands
are named by adding
o to the stem of the usual name, such
2-.
as chloro for Cl and sulfato for SO4
e. The name of each ligand is preceded by a Latin prefix (di-, tri- tetra-, penta,
hexa- etc.) if more than one of
that ligand Is bonded to the cetnral atom. For
2example, the ligands in PtCl4 are named tetrachloro, and the ligands in
Co(NH3)4Cl2+ are named tetraamminedichloro.
If the ligand is polydentate, as in ethylenediamine, the number of ligands
bonded to the central atom is indicated by the corresponding Greek prefixes
(bis-, tris-,
tetrakis-, pentakis-, hexakis-, etc.). For example, the ligands in
3+
Co(en)3 are named trisethylenediamine. A Greek prefix is also used when a
Latin prefix forms a part of the name of the ligand, as in triethylamine,
N(CH3)3. In this case, the ligand name is enclosed in parentheses. For
example, the ligands in [Co(N(CH3)3)4]2+ are named tetrakis(triethylamine).
4,
For a cationic complex ion or a nonionic compound, the central atom is given its
ordinary name followed by its oxidation 2+
number n Roman numerals, enclosed in
parentheses. For example, [Cr(H2O)5Cl] is named
pentaaquachlorochromium(III) ion, and [Cr(NH 3)3Cl3] is name

Name the following complex ions.


a. Ru(NH3)5Cl2+
b. Fe(CN)64c. Mn(NH2CH2CH2NH2)32+
d. Co(NH3)5NO22+
Name the following coordination compounds.
a. [Co(NH3)6]Cl2
b. [Co(H2O)6]I3
c. K2 [PtCl4]
d. K [PtCl ]

Give the formulas for the following.


a. Hexakispyridinecobalt(III)chloride
b. Pentaammineiodochromium(III) iodide
c. Trisethylenediamminenickel(II)bromide
d. Potassium tetracyanonickelate(II)
e. Tetraamminedichloroplatinum(IV)
tetrachloroplatinate(II)
Draw geometrical isomers of each of the
following complex ions.
a. [CO(C2O4)2(H2O2]b. [Pt(NH3)4I2]2+
c. [Ir(NH3)3Cl3]

Amino acids can act as ligand toward transition


metal ions. The simplest amino acid is glycine
(NH2CH2CO2H). Draw a structure of the glycinate
anion (NH2CH2CO2-) acting as a bidentate ligand.
Draw the structure isomers of the square planar
complex Cu(NH2CH2CO2)2.
BAL is a chelating agent used in treating heavymetal poisoning. It acts as a bidentate ligand. What
types of linkage isomers are possible when Bal
coordinates to a metal ion?

Geometrical Isomers of [Co(NH3)4Cl2]+

Geometrical isomers of [pt(NH3)2Cl2]

Mirror images of cis-[Co(en)2Cl2]+ and trans-[Co(en)2Cl2]+

COORDINATION
COMPOUND REACTIONS
Oxidation Reduction
Outer sphere: coordination sphere
and ligands do not change.
Inner sphere: one or more
coordination sphere changes.
Substitution Reactions (Displacement)
Ligand reactions

COORDINATE COVALENT
BONDS AND GEOMETRY
Valence Bond Theory
versus
Crystal Field Theory
Valence Bond
hybridization
Octahedral
d2sp3
Tetrahedral
sp3
Square planar
dsp2
low spin and high spin complexes

The 6 ligands in an octahedral crystal field

Formation of d2sp3 orbitals

Draw the d-orbital splitting diagrams for the


octahedral complex ions of each of the
following.
a. Fe2+ (high and low spin)
b. Fe3+ (high spin)
c. Ni2+
d. Zn 2+
e. Co2+ (high and low spin)
How many unpaired electrons are in the
following complex ions?
a. Ru(NH3)62+ (low-spin case)
b. Fe(CN)63- (low-spin case)
2+

The 4 ligands in a tetrahedral crystal field

Tetrahedral crystal field splitting energy

The d
orbital
energy
level
diagram
for an
octahedral
complex

Free Co
orbitals

The d
energy
diagrams
for square,
planar,
and linear
complexes

Spectra of emerald and ruby

Absorption and emission of light


by Cr (III) complex ions

Spectrochemical Series of Ligands

Ligand
CO
CN-NO2en
-NCNH3
-NCSOH2
C2O42-ONOOH-ONO2FCl-SCNS2BrI-

Wavelength in nm
of Peak in Spectrum
of Co(NH3)4X* (nm)

Crystal Field
Splitting Energy
for Co(NH3)5X (kJ/mol)

440
458

272
261

475
496
490

252
241
244

491
503
500
510
533

244
238
239
235
224

550
580

217
206

Large
Pairing
Energy

Small

The complex ion NiCl42- has two unpaired


electrons, while Ni(CN)42- is diamagnetic.
Propose structures for these two complex ions.

Tetrahedral complexes of Co2+ are quite


common. Use a d-orbital splitting diagram to
rationalize the stability of Co2+ tetrahedral
complex ions.

The compound Ni(H2O)6Cl2 is green, while


Ni(NH3)6Cl2 is purple. Predict the predominant
color of light absorbed by each compound. Which
compound absorbs light with the shorter
wavelength? Predict in which compound is
greater and whether H2O or NH3 is a stronger field
ligand. Do your conclusions agree with the
spectrochemical series?

The complex ion Fe(CN)63- is paramagnetic with one


unpaired electron. The complex ion Fe(SCN) 63- has
five unpaired electrons. Where does SCN - lie in the
spectrochemical series relative to CN -?