Chapter I-a

Coordination Chemistry, Chapter I
Copyright Xile Hu 1
Chapter I – Coordination Complexes: Definitions, Structure, Nomenclature, and Isomer
1. What are coordination compounds
In your previous courses, you have learned organic compounds like H2, CH4, and C2H6. You
have seen the structure of NaCl, where Na+ cations and Cl- anions are arranged in a 3-
dimensional lattice. Now you are about to learn a new class of compounds.
Definition (!!): Coordination compounds, or Complexes, are compounds that are composed of
a metal center and one or more ligands that formally donate electrons to the metal.
The metal center can be positively or negatively charged, or neutral.
The ligand can be an atom, an ion, or a molecule.
The metal can be any metal in the periodic table; in this class we focus on d-block metals.
12 345678
1 S P
2
D
3
4 3d
5 4d
6 5d
7 6d
F
4f
5f
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Example:
Cl
H3N Cl
Co
H3N NH3
Cl
Metal: Co
Ligands: NH3, Cl-.
(how many ligands for one Co center?)
Charge of complex: 0 (neutral)
The bonds "Co-Cl", "Co-NH3" are called Coordination Bonds.
In this complex, ligands (Cl- and NH3) donate electrons to Co by lone-pair electrons.
Another example.
Metal: Fe.
Ligands: H2O
Counter ion: SO42- (anion)
Charge of complex: 2+ (to keep the whole compound neutral)
The complex is positively charged.
Fe, six H2O, and the six Fe-OH2 coordination bonds constitute a Coordination Sphere. One can
say that the coordination sphere is +2 charged.
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Definition (!!): Coordination Number of a metal center is the number of atoms directly
attached to the metal center.
So for the previous two examples, the coordination number is 6.
Exercise.
Cl Cl
H3N Cl Cl
Co Co
H3N NH3 NH3
Cl Cl
(1) Is it a coordination compound?
(2) What are the ligands for each Co center?
(3) What is the coordination numbers for each Co center?
(4) What is the coordination sphere?
By definition, even the polymeric compound PdCl2 is a coordination compound. There are
infinite numbers of metal centers in PdCl2. Most studies in coordination chemistry however deal
with complexes with finite numbers of metal centers, except in the field of "coordination
polymer". In our class, we also focus on complexes with limited numbers of metal centers.
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2. Oxidation states and d electron counting of metal centers
For a complex [MLx]n, that is, a complex with a metal center coordinated by x number of
ligands, and with an overall charge of n, the following equations are valid:
Oxidation State (O.S.) of metal + overall charge of Lx = n (1.1)
Number of d electrons of metal = group number (periodic table) – O.S. (1.2)
Examples.
Cl
H3N Cl
Co
H3N NH3
Cl
Exercise.
What are the oxidation states and numbers of d electrons of the metal centers in the following
complexes?
(1) Cr(NH3)3Cl3
(2) [Fe(H2O)6]SO4
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3. Examples and geometries of coordination compounds, classified by coordination
numbers
The coordination number of a complex can range from 1 to more than 10. Among all
coordination compounds, 6-coordinate complexes are the most abundant.
¾ Coordination number of 7 and higher
Complexes with a coordination number of 7 or higher exist, but they are less frequent. Most of
these complexes have lanthanide or main group metal ions. Here I show you two examples.
The Y (Yttrium) ion has a coordination number of 8. Green balls represent F; Red balls represent
O; Blue balls represent N. This is so-called ball-stick drawing of the structure of a complex.
The Nd (Neodymium) ion has a coordination number of 10. The abbreviation 18C16 stands for
18-Crown-6, a crown ether ligand.
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¾ Coordination number of 6
For 6-coordinate complexes, the most common Coordination Geometry is Octahedral. For
examples, our familiar Co and Fe complexes below both have an octahedral geometry.
Cl
H3N Cl
Co
H3N NH3
Cl
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For your information. Some 6-coordinate complexes have a structure that is slightly deviated
from the ideal octahedral geometry. The most common deviations are tetragonal and trigonal
distortions.
Tetragonal distortion: elongation or compression along the 4-fold axis of the original octahedron.
Compression is along the 4-fold axis of the octahedron.
B
B
B B
B B
B
B
A
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Trigonal distortion: elongation or compression along the 3-fold axis of the original octahedron
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For 5-coordinate complexes, the two most common geometries are trigonal bipyramidal and
square pyramidal.
Trigonal bipyramial:
Square pyramidal:
Some 5-coordinate complexes have geometries in between ideal trigonal bipyramidal and square
pyramidal. We often designate their geometries as either distorted trigonal bypyramidal or
distorted square planar, depending on which geometry is closet to theirs.
Cl-: chloro, anionic ligand
CN-: cyano, anionic ligand
Exercise: what are the oxidation states of the two metal ions here?
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These are the second most popular class of complexes. For 4-coordinate complexes, the two
most common geometries are square planar and tetrahedral.
Square planar:
NMe2
N Ni Cl
NMe2
cis-platin nickamine
Tetrahedral: just like 4-coordinate organic compounds
Here, CO is a carbon monoxide ligand. It is neutral, and is often called "carbonyl". It is a
common ligand and very important for your Organometallic Chemistry class.
The metal centers in 3-coordinate complexes often have 10 d electrons. The most common
geometry is trigonal planar.
The ligand, PPh3, is triphenylphosphine. PR3, where R is an organic group, is called phosphine.
It is a very important class of ligand. It is a neutral ligand, and it donates the lone-pair electrons
on the phosphorus to the metal center.
Ph
M P Ph
Ph
There are not many complexes with a coordination number of 2. The 2-coordinate complexes are
mostly d10 metal complexes with big ligands. The geometry is linear.
It is very rare to see a complex with a coordination number of 1. They normally have huge
ligands.
¾ For your information. If you are interested seeing more examples of coordination
compounds, read pages 325-333 of the reference book.
4. Examples of some common ligands
Now that you know what coordination compounds are, know about the coordination geometries
and coordination numbers, let's see some common ligands.
¾ Mono-dentate ligands.
Ligands with only one point of attachment to the metal center.
Charged ligands:
F-: fluoro; Cl-: chloro; Br-; bromo; I-: iodo.
CN-: cyano; HO-: hydroxo; N3-: azido; SCN-: thiocyano; NH2-: amido.
Neutral ligands:
CO: carbonyl; H2O: aqua; PR3: phosphine; NH3: ammine; : pyridine
¾ Chelating ligands.
Definiation (!!): Ligands with two or more points of attachment to metal atoms are called
chelating ligands
Bidentate: a ligand has two points of attachment to metal.
Tridentate: a ligand has three points of attachment to metal.
Tetradentate: a ligand has four points of attachment to metal.
Pentadentate: a ligand has five points of attachment to metal.
Hexadentate: a ligand has six points of attachment to metal.
Polydentate: a ligand has more than two points of attachment to metal.
Examples.
Common name: ethylenediamine; Abbreviation: en
"en" is a very popular bidentate ligand. It coordinates to a metal center by its two nitrogen
atoms.
Common name: 2,2-bipyridine; Abbreviation: bipy.
Common name: 1,10-phananthroline; Abbreviation: phen.
Common name: terpyridine; Abbreviation: terpy.
N N
H
N N N N
H
N N
Common name: porphyrin (left). When it coordinates to a metal ion, it normally loses 2 proton,
to form porphyrinate (right).
Porphyrin is an important biological ligand.
One of the best known porphyrin is heme, present in your blood. Heme (below) is a Fe
porphyrinate complex that carries your oxygen.
Common name: enthylenediaminetetraacetato; Abbreviation: EDTA
edta [Y(edta4-)F2]3-
EDTA is a very strong chelating ligand. It is often used in biological studies to extract trace
amount of metal ions.
O
O O
O O
O
Common name: 18-crown-6; Abbreviation: 18C6.
Exercise.
Judge which ligands in the following complexes are chelating ligands. Are they bi-, tri-, tetra-, or
hexa-dentate?
(1)
NH HN
Cl Fe Cl
HN NH
(2)
What is the coordination number in (2)?
(3)
Here the acetate ligands are bridging.
5. Nomenclature of coordination compounds.
The International Union of Pure and Applied Chemistry (IUPAC) has set up rules for the
nomenclature of coordination compounds. In practice, many common names and abbreviation
are widely used. (For your information. See pages 307-309 of the reference book if you are
interested in knowing the complete rules.) Here I list the most important rules.
1. The coordination sphere is enclosed in square brackets in the formula.
[Ag(NH3)2]Cl; K3[Fe(CN)6)].
2. The number of ligands of one kind is given by the first set of prefixes. If the name includes
already these prefixes or is complicated, then the second set of prefixes is used in conjunction of
a parenthesis for the name of the ligand.
Number of ligands First set of prefixes Second set of prefixes
2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis
Examples.
[Co(NH2CH2CH2NH2)2Cl2]+ = dichlorobis(ethylenediamine)...
2+
N
N N
Fe
N N
N
= tris(bipyridine)...
3. There are two possibilities for designating the charge or the oxidation state.
(a) Put the oxidation state as a Roman numeral in parenthesis after the name of the metal.
(2) Put the charge of the coordination sphere in parenthesis after the name of the metal; in case
the charge is negative, the suffix –ate is added to the name of the coordination sphere.
[Pt(NH3)4]2+ = tetraammineplatinum(II) = tetraammineplatinum(2+)
[PtCl6]2- = hexachloroplatinate(IV) = hexachloroplatinate(2-)
4. Prefix cis- and trans- designate adjacent and opposite geometric locations.
[Pt(NH3)2Cl2]
cis-diamminedichloroplantium(II) trans-diamminedichloroplantium(II)
These two platinum complexes are cis/trans isomers.
Definition (!!): Isomers are two or more complexes having the same chemical compositions but
different chemical and physical properties.
5. Bridging ligands between metal ions have the prefix "μ-"
μ-amido-μ-hydroxobis(tetraamminecobalt)(4+)
Exercise.
Give chemical names for the following.
a. [Cu(NH3)4]2+
b. [PtCl4]2-
c. [Co(en)3]3+
6. Isomers
Isomers are two or more complexes having the same chemical compositions but different
chemical and physical properties.
Isomers can be classified as constitutional isomers and stereoisomers.
Q: How to judge whether the isomers belong to constitutional isomers or stereoisomers?
A: For two or more molecules with identical chemical formula, if all the chemical bonds are
between the same atoms, then they are stereoisomers (or the same molecules). If not all the
chemical bonds are between the same atoms, then they are constitutional isomers.
¾ Constitutional Isomers
(a) Hydrate isomer
Hydrate isomers exist for complexes that have water either as a ligand or as an added part of the
crystal structure. The standard example is CrCl3•6H2O. Three distinct crystalline compounds
exist with the same formula. They are:
[Cr(H2O)6]Cl3 (violet)
[Cr(H2O)5Cl]Cl2•H2O (blue-green)
[Cr(H2O)4Cl2]Cl•2H2O (dark green)
These are hydration isomers.
¾ (b) Ionization isomers.
Compounds with the same formula but give different ions in solution, exhibit ionization
isomerization. The difference is in which ion is included as a ligand and which is presented to
balance the overall charge.
Examples.
[Co(NH3)4(NO2)Cl]Cl and [Co(NH3)4Cl2]NO2
[Co(NH3)4Cl2]Br and [Co(NH3)4ClBr]Br
¾ (c) Linkage isomers
Some ligands can bind to the metal through different atoms. For example, thiocyanate (SCN-)
can bond to metal through either S or N. Nitrite (NO2-) can bond to metal through either N or O.
NH3 2+ NH3 2+
H3N NH2 H3N NH2
h
Co Co
O
H3N N H3N O
N O
NH3 O NH3
yellow red
¾ (d) Coordination isomerism
To have coordination isomers, the complexes have at least two metal ions. The total ratio of
ligand to metal remains the same, but the ligands attached to a specific metal ion change. This is
best described by example.
[Co(en)3][Cr(CN)6] and [Cr(en)3][Co(CN)6]
[Pt(NH3)4][PtCl6] and [Pt(NH3)4Cl2][PtCl4]
In general, for constitutional isomerism, it is not important to know exactly what kind of
isomerism the isomers belong to. It is however important to be able to know whether two or
more complexes are isomers, and to draw the structures of possible isomers if you are given a
chemical formula.
Exercise.
Which of the following pairs are isomers.
(a) [Co(H2O)5Cl]Br and [Co(H2O)4ClBr]•H2O
(b) [Co(NH3)4Cl2]Br and [Co(NH3)4ClBr]Cl
(3) [Co(NH3)6]ClBr and [Co(NH3)6]BrCl
¾ Stereoisomers
Stereoisomers in coordination chemistry are molecules with identical formula and have the same
bonds between the same atoms. They can be classified as geometric isomers and enantiomers.
If each isomer is identical to its mirror image, then they are geometric isomers. If each isomer is
not identical to its mirror image, then they are enantiomers.
Geometric isomers
Cis/trans-isomers and facial/meridional isomers are the most common geometric isomers.
Let's look at 4- and 6-coordinate compounds.
For 4-coordinate complexes, if two of the ligands are the same, then there are two situations.
For square planar complexes, there are the possibilities of having cis-/trans- isomers.
cis-diamminedichloroplantium(II) trans-diamminedichloroplantium(II)
The cis/trans isomers can have very different properties. For example, cis-
diamminedichloroplantium(II) is an anti-cancer agent, while trans-
diamminedichloroplantium(II) has no anti-cancer activity.
For tetrahedral complexes, there is no possibility of having cis-/trans-isomers.
Cl
PPh3
Ni
Cl PPh3
For 6-coordinate complexes, it is possible to have cis-/trans- isomers.
Cl Cl
H3N NH3 H3N Cl
Co Co
H3N NH3 H3N NH3
Cl NH3
trans-isomer cis-isomer
For 6-coordinate complexes, if three ligands are the same, it is possible to have facial-
/meridional isomers.
Cl Cl
H3N Cl H3N Cl
Co Co
H3N NH3 H3N Br
Br NH3
meridional isomer facial isomer
mer- fac-
The following are also geometry isomers:
a a
f c f c
M M
d e e d
b b
Exercise: write the possible geometric isomers for [Co(NH3)3Cl2(H2O)]

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Coordination Chemistry, Chapter I

Chapter I – Coordination Complexes: Definitions, Structure, Nomenclature, and Isomer

1. What are coordination compounds

The metal center can be positively or negatively charged, or neutral.

The ligand can be an atom, an ion, or a molecule.

Ligands: NH3, Cl-.

(how many ligands for one Co center?)

Charge of complex: 0 (neutral)

The bonds "Co-Cl", "Co-NH3" are called Coordination Bonds.

Counter ion: SO42- (anion)

Charge of complex: 2+ (to keep the whole compound neutral)

The complex is positively charged.

say that the coordination sphere is +2 charged.

attached to the metal center.

So for the previous two examples, the coordination number is 6.

H3N NH3 NH3

(1) Is it a coordination compound?

(2) What are the ligands for each Co center?

(3) What is the coordination numbers for each Co center?

(4) What is the coordination sphere?

2. Oxidation states and d electron counting of metal centers

Oxidation State (O.S.) of metal + overall charge of Lx = n (1.1)

Number of d electrons of metal = group number (periodic table) – O.S. (1.2)

3. Examples and geometries of coordination compounds, classified by coordination

coordination compounds, 6-coordinate complexes are the most abundant.

¾ Coordination number of 7 and higher

18-Crown-6, a crown ether ligand.

Compression is along the 4-fold axis of the octahedron.

pyramidal. We often designate their geometries as either distorted trigonal bypyramidal or

distorted square planar, depending on which geometry is closet to theirs.

Cl-: chloro, anionic ligand

CN-: cyano, anionic ligand

most common geometries are square planar and tetrahedral.

Tetrahedral: just like 4-coordinate organic compounds

Here, CO is a carbon monoxide ligand. It is neutral, and is often called "carbonyl". It is a

geometry is trigonal planar.

on the phosphorus to the metal center.

compounds, read pages 325-333 of the reference book.

4. Examples of some common ligands

and coordination numbers, let's see some common ligands.

Ligands with only one point of attachment to the metal center.

F-: fluoro; Cl-: chloro; Br-; bromo; I-: iodo.

CO: carbonyl; H2O: aqua; PR3: phosphine; NH3: ammine; : pyridine

Bidentate: a ligand has two points of attachment to metal.

Tridentate: a ligand has three points of attachment to metal.

Tetradentate: a ligand has four points of attachment to metal.

Pentadentate: a ligand has five points of attachment to metal.

Hexadentate: a ligand has six points of attachment to metal.

Polydentate: a ligand has more than two points of attachment to metal.

Common name: ethylenediamine; Abbreviation: en

Common name: 2,2-bipyridine; Abbreviation: bipy.

Common name: 1,10-phananthroline; Abbreviation: phen.

Common name: terpyridine; Abbreviation: terpy.

to form porphyrinate (right).

Porphyrin is an important biological ligand.

porphyrinate complex that carries your oxygen.

Common name: enthylenediaminetetraacetato; Abbreviation: EDTA

amount of metal ions.

Common name: 18-crown-6; Abbreviation: 18C6.

What is the coordination number in (2)?