Chemistry of Coordination

(Complex) Compounds

Chemistry of
Coordination
Compounds
What are the Complexes?
• This is a compound, which
consists of three structural
units:
• (1) – central atom or ion
possessing some free
unoccupied valent orbitals
• (2) – a group of molecules or
ions (ligands) possessing free
unbound electron pairs
associated with (1)
• (3) some outer
counterbalancing ions, which
balance excessive charge (if
any) of the units (1) and (2)
Chemistry of
Coordination
Compounds
 Why important?

• Enzymes? Complexes!
• Proteins? Often = complexes!
• Hemoglobin, chlorophyll, vitamins (B6,
B12, etc) = complexes!
• Detoxification agents? Complexes!
• Many medicines = complexes!
• Many poisons = complexes! Chemistry of
Coordination
Compounds
Hemoglobin and CO
O2

CO
Chemistry of
Coordination
Compounds
 CO poisoning

• Red (later bluish) skin and lips

• Dangerous but reversible

Chemistry of
Coordination
Compounds
 Cyanides… Detoxification…

• A mechanism of cyanides toxicity is

similar: formation of some strong
complex compounds, which can block
some vital proteins, enzymes, etc.
• Detoxification by the complexes?
• Similar! An antidote forms a strong
complex compound to be removed from
the human organism…
Chemistry of
Coordination
Compounds
 Complexes

• The molecules or ions coordinating to the

metal are the ligands. (Unit (2))
• They are usually anions or polar molecules.

Chemistry of
Coordination
Compounds
 Metal-Ligand Bond
• This bond is formed by the donor-acceptor
mechanism
 The ligands always have nonbonding electrons.
 The complexation agent (metal) has unoccupied
orbitals
 This way the complex particle is being formed
 It is quite stable and can exist as a whole particle

Chemistry of
Coordination
Compounds
How to calculate charge of a complex
Complex charge = sum of charges
on the metal and the ligands

[Fe(CN)6]3-

Chemistry of
Coordination
Compounds
Complex charge = sum of charges
on the metal and the ligands

[Fe(CN)6]3-

+3 6(-1)

Chemistry of
Coordination
Compounds
 Neutral charge of coordination compound = sum of
charges on metal, ligands, and counterbalancing ions

[Co(NH3)6]Cl2

neutral compound

Chemistry of
Coordination
Compounds
 Neutral charge of coordination compound = sum of
charges on metal, ligands, and counterbalancing ions

[Co(NH3)6]Cl2

+2 6(0) 2(-1)

Chemistry of
Coordination
Compounds
Coordination Number
• CN is an amount of ligands
bonded to the central
particle
• Usually (not always!) it is
even and equal to the
double charge of the central
ion
• Some metals, such as Cr(III)
and Co(III) have the same
coordination number in all
their complex compounds (6
in the case of these two
metals).
• The most common CN are 4
and 6.
Chemistry of
Coordination
Compounds
 Common Geometries of Complexes

Coordination Number Geometry

Linear
Example: [Ag(NH3)2]+

Chemistry of
Coordination
Compounds
 Common Geometries of Complexes
Coordination Number 4 Geometry
tetrahedral
Examples: [Zn(NH3)4]2+, [FeCl4]-

Example: [Ni(CN)4]2-
Chemistry of
Coordination
flat square planar Compounds
 Common Geometries of Complexes
Coordination Number Geometry
6

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

octahedral Chemistry of
Coordination
Compounds
 Classifications of Complexes

• Ligands’ nature
 classified according to the number of donor-
acceptor bonds that can be formed by each ligand
molecule or ion
 Examples
• monodentate = 1
• bidentate = 2
• tetradentate = 4
• hexadentate = 6
• 2 or more donor atoms = polydentate
Chemistry of
Coordination
Compounds
 Classification of Complexes
• Ligands
Examples
• monodentate = 1
chelating agents
• bidentate = 2
• tetradentate = 4
• hexadentate = 6
• polydentate = 2 or more donor atoms

Chemistry of
Coordination
Compounds
 Ligands
• Monodentate
 Examples:
• H2O, CN-, NH3, NO2-, SCN-, OH-, X- (halogens),
CO, O2-
Example Complexes
• [Co(NH3)6]3+
• [Fe(SCN)6]3-

Chemistry of
Coordination
Compounds
 Ligands
• Bidentate
Examples
• oxalate ion = C2O42-
• ethylenediamine (en) = NH2CH2CH2NH2
• ortho-phenanthroline (o-phen)
Example Complexes
• [Co(en)3]3+ - six bonds formed!
• [Cr(C2O4)3]3- - six bonds formed!
• [Fe(NH3)4(o-phen)]3+ - six bonds formed!

Chemistry of
Coordination
Compounds
 Ligands
oxalate ion Donor Atoms
ethylenediamine
O O 2-
CH2 CH2
C C
H2N NH2
O O * *
* *
ortho-phenanthroline
CH
*N CH
*
N C CH
Donor Atoms HC C C

HC C CH
CH CH Chemistry of
Coordination
Compounds
 Polydentate Ligands
• Some ligands have two
or more donor atoms.
• These are called
polydentate ligands or
chelating agents.
• In ethylenediamine,
NH2CH2CH2NH2,
represented here as en,
each N is a donor atom.
• Therefore, en is Chemistry of
bidentate. Coordination
Compounds
Polydentate Ligands

Ethylenediaminetetraacetate,
mercifully abbreviated EDTA,
has six donor atoms.

Chemistry of
Coordination
Compounds
 Polydentate Ligands
• Chelating agents generally form more stable
complexes than do monodentate ligands
• Why?
• Each particle forms more bonds than one…
• More ‘hands’ = stronger capturing…

Chemistry of
Coordination
Compounds
Chelating Agents
• Therefore, they can
render metal ions
inactive without actually
removing them from
solution
• Polyphosphates are
used to tie up Ca2+ and
Mg2+ in hard water to
prevent them from
interfering with
detergents Chemistry of
Coordination
Compounds
 Chelating antidotes

• Same approach is
used often to prevent
or relief negative
effects of poisoning by
heavy metals ions
• They will be effectively
captured by chelating
ligands and isolated in
the organism tissues
and blood-vascular
system
• EDTA is a commonly
used antidote Chemistry of
Coordination
Compounds
Chelating Agents in Biology/Medicine

Porphyrines (like
hemoglobin or
chlorophyll) are
tetradentate ligands.

Chemistry of
Coordination
Compounds
Metalloporphyrin (hemoglobin)

N
2+
N Fe N

Chemistry of
Coordination
Compounds
Myoglobin, a protein that
stores O2 in cells

Chemistry of
Coordination
Compounds
 Nomenclature of Coordination
Compounds (how to name a ligand)
• The basic protocol in coordination nomenclature
is to name the ligands attached to the metal as
prefixes before the metal name.
• Some common ligand ions and their names are
listed in the next slides
• The general rule is to end an anion with “o”:
• Bromide = bromido; sulfate = sulfate; silicate =
silicato…

Chemistry of
Coordination
Compounds
Nomenclature: IUPAC Rules
Ligand Name
bromide, Br- Bromido (bromo)
chloride, Cl- Chlorido (chloro)
cyanide, CN- Cyanido (cyano)
hydroxide, OH- hydroxo
oxide, O2- oxo
fluoride, F- Fluorido (fluoro)

Chemistry of
Coordination
Compounds
Nomenclature: IUPAC Rules
Ligand Name
carbonate, CO32- carbonato
oxalate, C2O42- oxalato
sulfate, SO42- sulfato
thiocyanate, SCN- thiocyanato
thiosulfate, S2O32- thiosulfato
Sulfite, SO32- sulfito

Chemistry of
Coordination
Compounds
 Nomenclature: IUPAC Rules
• Neutral ligands are referred to by the
usual name for the molecule
Example
• ethylenediamine
Exceptions
• water, H2O = aqua
• ammonia, NH3 = ammine
• carbon monoxide, CO = carbonyl

Chemistry of
Coordination
Compounds
 Nomenclature: IUPAC Rules
• If a complex is cation, its name stays unchanged
• If a complex is an anion, its name ends with the
-ate appended to name of the metal

Transition Metal Name if in Cationic Complex Name if in Anionic Complex

Sc Scandium Scandate
Ti titanium titanate
V vanadium vanadate
Cr chromium chromate
Mn manganese manganate
Fe iron ferrate
Co cobalt cobaltate
Ni nickel nickelate
Chemistry of
Cu copper cuprate
Coordination
Zn zinc zincate Compounds
 Nomenclature of Coordination
Compounds
• As in the case with ionic compounds, the name of the
cation appears first; the anion is named last.
• Ligands are listed alphabetically before the central metal
• In case of a complex acid or base, the complex particle
should be named first then the word ‘acid’ or ‘hydroxide’
should be added
• [Co(NH3)5Cl]Cl2 – pentaamminechloridocobalt(III) chloride

Chemistry of
Coordination
Compounds
 Some examples

• K4[Fe(CN)6] – potassium hexacyanoferrate(II)

• K3[Fe(CN)6] – potassium hexacyanoferrate(III)
• [Cu(NH3)4](OH)2 – tetraamminecopper hydroxide
• H2[PtCl6] – hexachloridoplatinate acid (or
hydrogen hexachloridoplatinate)
• [Co(NH3)5Cl]Br – pentaamminechloridocobalt(II)
bromide
• [Co(NH3)4(H2O)Br]Cl –
tetraammineaquabromidocobalt chloride Chemistry of
Coordination
Compounds
 Some more examples

• Na2[Zn(OH)4]
• Sodium tetrahydroxozincate
• and no more details on zinc valence are
required…
• K3[Fe(OH)6]
• Potassium hexahydroxoferrate(III)
• Na2[Be(OH)4]
• Sodium tetrahydroxoberillate Chemistry of
Coordination
Compounds
 Some more examples

• [Zn(NH3)4](OH)2
• Tetraaminezinc hydroxide
• H[AuCl4]
• Tetrachloridoaurate acid (or hydrogen
tetrachloridoaurate)
• [Co(NH3)5Br]Cl
• Pentaaminobromidocobalt(II) chloride Chemistry of
Coordination
Compounds
 Isomerization of Complexes

Isomers have the same molecular formula, but

their atoms are arranged either in a different order
(structural isomers) or spatial arrangement Chemistry of
(stereoisomers). Coordination
Compounds
 Structural Isomers

If a ligand (like
the NO2 group at
the bottom of
the complex)
can bind to the
metal with one
or another side
as the donor
atom, linkage
isomers are
formed. Chemistry of
Coordination
Compounds
 Structural Isomers
• Some isomers differ in what ligands are
bonded to the metal and what are
outside the coordination sphere; these
are coordination-sphere isomers.
• Three isomers of CrCl3(H2O)6 are
The violet [Cr(H2O)6]Cl3,
The deep green [Cr(H2O)5Cl]Cl2 ∙ H2O, and
The light green [Cr(H2O)4Cl2]Cl ∙ 2 H2O.
Chemistry of
Coordination
Compounds
Coordination-Sphere Isomers
• Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
• Consider ionization (dissociation) in
water
[Co(NH3)5Cl]Br  [Co(NH3)5Cl]+ + Br-

[Co(NH3)5Br]Cl  [Co(NH3)5Br]+ + Cl-

Chemistry of
Coordination
Compounds
 Coordination-Sphere Isomers
• Example
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
• Consider precipitation
[Co(NH3)5Cl]Br(aq) + AgNO3(aq)  [Co(NH3)5Cl]NO3(aq) + AgBr
(yellowish sediment)

[Co(NH3)5Br]Cl(aq) + AgNO3(aq)  [Co(NH3)5Br]NO3(aq) + AgCl

(white sediment)

Chemistry of
Coordination
Compounds
 Stereoisomers
• With these geometric
isomers, two chlorines
and two NH3 groups
are bonded to the
platinum metal, but are
clearly different.

cis-isomers have like groups on the same side.

trans-isomers have like groups on opposite sides.

Chemistry of
Coordination
Compounds
 Stereoisomers

• Other stereoisomers, called optical isomers or

enantiomers, are mirror images of each other.
• Just as a right hand will never fit into a left glove,
two enantiomers cannot be superimposed on Chemistry of
each other. Coordination
Compounds
 Enantiomers

A molecule or ion that exists as a pair of

enantiomers is said to be chiral.

Chemistry of
Coordination
Compounds
 Dissociation of complexes

• Any soluble complex ionic compound

undergoes complete irreversible primary
dissociation into the complex ion and
outer ions (single step):
K 4 [ Fe(CN ) 6 ]  4 K   [ Fe(CN ) 6 ] 4
[Co( NH 3 ) 5 Cl ]Br  [Co( NH 3 ) 5 Cl ]   Br 

Chemistry of
Coordination
Compounds
 Dissociation of complexes
• Second stage of dissociation affects the
complex ion itself:
 2 
[Co( NH 3 ) 5 Cl ]  Co  5 NH 3  Cl
• This is always the reversible
(equilibrium process) and the
equilibrium shifting can be represented
by the complex ion instability constant:
C (Co 2 )C 5 ( NH 3 )C (Cl  )
K compl 
C ([Co( NH 3 ) 5 Cl ]  ) Chemistry of
Coordination
Compounds
 Dissociation of complexes

• The higher is the complex instability constant

value, the lower is stability of the complex ion
• Many complex ions are quite stable and form
very strong bonds with the metal ions
[ Ag ( NH 3 ) 2 ]  Ag   2 NH 3
• Concentration of free silver ions in the above
system is so low that formation of insoluble
AgCl doesn’t take place… (but AgI can be
formed)…
Chemistry of
Coordination
Compounds
Video-summary

Chemistry of
Coordination
Compounds
 Next topic:

• Solution concentrations…

Chemistry of
Coordination
Compounds