Ch.

7: 1
Chapter 7: An introduction to coordination compounds
1. Ligand an ion or molecule that can have an independent existence
2. Coordination compound a neutral complex or an ionic compound in which at least one
of the ions is a complex
a. A complex is a combination of a Lewis acid (the central metal atom) with a number
of Lewis base (the ligands)
3. Donor atom the atom in the Lewis base ligand that forms the bond to the central atom,
it donates the electron used in bond formation
4. Acceptor atom the metal atom or ion, the Lewis acid in the complex
a. All metals, from all blocks of the periodic table, form complexes
5. The language of coordination chemistry
a. Inner-sphere complex the ligands are attached directly to the central metal
atom or ion
b. Primary coordination sphere formed by the ligands directly attached to the
central metal atom or ion
c. Coordination number the number of ligands directly attached to the central
metal or atom
d. Outer-sphere complex complex cations can associate electrostatically with ionic
ligands (and, by other weak interactions, with solvent molecule) without
displacement of the ligands already present
6. 7.1 Representative ligands
a. Monodentate ligands that only have a single donor pair of electrons and will
have only one point of attachment to the metal
b. Polydentate ligands that have more than one point of attachment
i. Bidentate two points of attachment
ii. Tridentate three points of attachment
c. Ambidentate have more than one different potential donor atom
i. NCS-, can attach to a metal atom either by the N atom
d. Chelates a complex in which a ligand forms a ring that includes the metal atom
i. Can be formed by polydentate ligands
ii. Example: (1,2-diaminoethane, en, NH2CH2CH2NH2), which forms a fivemembered ring when both N atoms attach to the same metal atom
iii. Normal chelating ligands will attach to the metal only at two adjacent
coordination sites in a cis fashion
iv. Complexes of chelating ligands often have additional stability over those of
non-chelating ligands the origin of this so called chelate effect
7. 7.2 Nomenclature cations are named first and ligands are named in alphabetical order
a. For compound that consist of one or more ions, the cation is named first followed by
the anion
b. Complex ions are named with their ligands in alphabetical order (ignoring any
numerical prefixes)
i. The ligand names are followed by the name of the metal with either its
oxidation number in parentheses
c. The number of a particular type of a ligand in a complex is indicated by the prefixes
mono-, di-, tri-, and tetrai. The same prefixes are used to state the number of metal atoms if more than
on is present in a complex
d. Square brackets are used to indicate which group are bound to a metal atom, and
should be used whether the complex is charged or not; however, in casual usage,
neutral complexes and oxoanions are often written without brackets

Ch. 7: 2
8. Constitution and geometry
a. Three factors govern the coordination number of a complex:
i. The size of the central atom or ion
ii. The steric interactions between the ligands
iii. Electronic interactions between the central atom or ion and the ligands
b. In general, the large radii of atoms and ions lower down the periodic table favour
higher coordination numbers
c. Lower coordination numbers are found on the right of the d block, particularly if the
ions are rich in electrons; and example is [PtCl4]29. 7.3 Low coordination numbers
a. Two-coordinate complexes are found for Cu+ and Ag+; these complexes often
accommodate more ligands if they are available
i. Ag(NH3)2+
ii. Linear
10.7.4 Intermediate coordinate numbers
a. Complexes of metal ions with the intermediate coordination numbers four, five, and
six are the most important class of complex. They include the vast majority of
complexes that exist in solution and almost all the biologically important complexes
b. Four-coordination
i. Tetrahedral complexes are favored over higher coordinate complex if the
central atom is small or the ligands large; square-planar complexes are
typically observed for metals with d8 configurations
ii. Tetrahedral complexes of approximately Td symmetry (14) are favoured over
higher coordination numbers when the central atom is small and ligands are
large (such as Cl-, Br-, and I-) because then ligand-ligand replusions override
the energy advantage of forming more metal-ligand bonds
iii. Another type of four-coordinate complex is also found: those where the four
ligands surround the central metal in a square-planar arrangement
1. Square-planar complexes with four identical symmetric ligands have
D4h symmetry

c. Five-coordination
i. Five-coordinate complexes, which are less common than four- or sixcoordinate complexes, are normally either square pyramidal or trigonal
bipyramidal
ii. Ligands that force a trigonal-bipyramidal structure in this fashion are called
tripodal

Ch. 7: 3

d. Six-coordination
i. Six-coordination is the most common arrangement for metal complexes and
is found in s-, p-, d-, and f-metal coordination compounds
ii. Almost all six-coordinate complexes are octahedral, at least if we consider the
ligands as represented by structure-less point

iii.
11.7.5 Higher coordination numbers
a. Larger atoms and ions, particularly those of the f block, tend to form complexes with
higher coordination numbers; nine-coordination is particularly important in the f
block
12.Polymetallic complexes
a. Polymetallic complexes are complexes that contain more than one metal atom
i. In some cases, the metal atoms are held together by bridging ligands; in
others there are direct metal-metal bonds; in yet others there are both types
of link
b. Metal cluster usually reserved for polymetallic complexes in which tehrea re
direct metal-metal bonds that form triangular or larger closed structures
i. Exclude linear M-M compounds, and is normally relaxed
ii. Any M-M bonded system is said to be a cluster
c. When no metal-metal bond is present, polymetallic complexes are referred to as
cage complexes or caged compounds
13.Isomerism and chirality a molecular formula may not be sufficient to identify a
coordination compound: linkage, ionization, hydrate, and coordination isomerism are all
possible for coordination compounds
a. Linkage isomerism in which the same ligand may link through different atoms
i. [(NH3)5CoNO2] Cl2 nitro
ii. [(NH3)5Co(O-NO)] Cl2 nitrito
b. Ionization isomerism occurs when a ligand and a counterion in one compound
exchange places
i. If the compounds are soluble, the two isomers exist as different ionic species
in solution
ii. [Co(NH3)5Br]2+ SO42iii. [Co(NH3)5SO4]+ Brc. Hydrate isomerism arises when one of the ligands is water
i. [Cr(OH2)6]Cl3 Violet
ii. [Cr(OH2)5]Cl]Cl2.H2O Blue-green

Ch. 7: 4
iii. [Cr(OH2)4Cl2]Cl.2H2O Green
d. Coordination isomerism arises when there are different complex ions that can
form from the same molecular formula
i. same metals same oxidation states
1. [Pt(NH3)4][PtCl4] ; [Pt(NH3)3Cl][Pt(NH3)Cl3]
ii. b) same metal different oxidation states
1. [Pt(NH3)4][PtCl4] ; [Pt(NH3)4Cl2][PtCl4]
iii. Different metals
1. [Co(NH3)6][Cr(CN)6] ; [Cr(NH3)6][Co(CN)6]
e. Geometric isomerism the varieties of isomerism by considering the
permutations of ligand arrangement for each of the common complex geometries
14.7.7 Square-planar complexes
a. In the simple case of two sets of two different monodentate ligands, as in [MA2B2],
there is only the case of cis/trans isomerism
b. With three different ligands, as in [MA2BC], the locations of the two A ligands also
allow us to distinguish the geometric ligands as cis and trans
c. When there are four different ligands, as in[MABCD], there are three different
isomers and we have to specify
d. Bidentate ligands with different endgroups, as in [M(AB)2], can also give rise to
geometrical isomers that can be classified as cis and trans
15.7.8 Tetrahedral complexes
a. The only isomers of tetrahedral complexes normally encountered are those where
either all four ligands are different or where there are two unsymmetrical bidentate
chelating ligands
i. In both cases, the molecules are chiral, not superimposable on their mirror
images
ii. Two mirror-image isomers jointly make up an enantiomeric pair
iii. Optical isomerism the existence of a pair of chiral complex that re each
others mirror image, and that have lifetimes that are long enough for them
to be separable
16.7.9 Trigonal-bipyramidal and square-pyramidal complexes
a. The conversion from one stereochemistry to another may occur by a Berry
pseudorotation
17.7.10 Octahedral complexes
a. [MA6] or[MA5B]
i. Only one way of arranging the ligands in octahedral
b. [MA4B2]
i. May be placed on adajacent octahedral positions to give a cis isomer or on
diametrically opposite positions to give a trans isomer
c. [MA3B3]
i. There are two ways of arranging the ligands
ii. In one isomer, three A ligands lie in one plane and three B ligands lie in a
perpendicular plane
1. Complex is designed the mer isomer because each set of ligands can
be regarded as lying a meridian of a sphere
iii. In the second isomer, all three A (and B) ligands are adjacent and occupy the
corners of one triangular face of the octahedron; this complex is designated
the fac isomer
iv. Provided we treat the ligands as structureless points, the mer isomer has C2v
symmetry and the fac isomer has C3v symmetry
d. [MA2B2C2]

Ch. 7: 5
i. There are five different geometrical isomers
1. All trans isomer; three different isomers where one pair of ligands are
trans with the other two cis
2. All enantiomeric pair of all-cis isomers
ii. More complicated, [MA2B2CD] or [MA3B2C]
1. Fac
2. Mer-trans
3. Mer-cis