COMPLEX IONS: PART 1
From left to right, aqueous solutions of:
Co(NO3)2 (red); K2Cr2O7 (orange);
K2CrO4 (yellow); NiCl2 (green);
CuSO4 (blue); KMnO4 (purple).
Coordination Complexes
• CuSO4· 5H2O, [FeCl4] - ion and CrCl3·6 NH3,
are called coordination complexes because
they contain ions or molecules linked (or
coordinated) to a transition metal.
• They are also known as complex ions
because they are Lewis acid-base complexes.
• The ions or molecules that bind to transition-
metal ions to form these complexes are called
ligands (from Latin, "to tie or bind").
• The number of ligands bound to the transition
metal ion is called the coordination number
WRITING THE FORMULA
• Use brackets to enclose the ion [not
always required]
• The metal is written first.
• The ligands follow, written in alphabetical
order.
• The charge of the ion is written outside of
the bracket.
METALS THAT FORM
COMPLEXES
• mostly transition metals
• some main group elements also form
complexes
• Aluminum, tin, and lead, for example, form
complexes such as the [AlF6]3-, [SnCl4]2-
and [PbI4]2- ions.
NAMING COMPLEX METAL IONS
• names of complex ions can look long and
complicated
• the formulas are simply being coded in the
same way that organic names are coded
• Once you have sorted out that code, the
names are entirely descriptive.
Naming the ligands
ligand coded by (old name)
H2O aqua aquo
NH3 ammine ammino
OH- hydroxo hydroxy
Cl- chloro
F- fluoro
CN- cyano
SCN- thiocyanato (bonded – S)
isothiocyanato (bonded – N)
• Take care with the code for ammonia as a
ligand - it has 2 "m"s in its name.
• "amine" or "amino", refers to the NH2
group in an organic compound.
Coding for the number of ligands
no of ligands coded by
2 di
3 tri
4 tetra
5 penta
6 hexa
Putting this together
• For a complex ion containing only one type of ligand,
there is no problem. For example:
• [Cu(H2O)6]2+ is called the hexaaquacopper(II) ion.
• The fact that there are two "a"s next to each other in the
name is OK.
• With more than one type of ligand in an ion, the ligands
are named in alphabetical order - ignoring the prefixes.
For example:
• [Cu(NH3)4(H2O)2]2+ is called the
tetraamminediaquacopper(II) ion.
• The "ammine" is named before the "aqua" because "am"
comes before "aq" in the alphabet. The "tetra" and "di" are
ignored.
Naming the metal
For positively charged complex ions
• A positively charged complex ion is called
a cationic complex. A cation is a
positively charged ion.
• The metal uses the English name with the
addition of its oxidation state.
Naming the metal
• [Cu(H2O)6]2+ is called the hexaaquacopper(II) ion
because the copper's oxidation state is +2.
• Copper's oxidation is +2 because the original
uncomplexed ion was Cu2+ - NOT because the
complex carries 2+ charges.
• The oxidation state is frequently left out if a metal
has one oxidation state.
• For example, in its compounds aluminum always
has an oxidation state of +3. [Al(H2O)6]3+ is usually
just called the hexaaquaaluminium ion rather than
the hexaaquaaluminium(III) ion.
Naming the metal
For negatively charged complex ions
• A negatively charged complex ion is called an
anionic complex. An anion is a negatively
charged ion.
• In this case the name of the metal is modified to
show that it has ended up in a negative ion. This
is shown by the ending -ate.
• With many metals, the basic name of the metal
is changed as well – the Latin root is used.
Naming the metal
metal Changed to
cobalt cobaltate
aluminum aluminate
chromium chromate
vanadium vanadate
copper cuprate
iron ferrate
lead plumbate
sliver argentate
• Suppose there are 4 chloride ions bonded
around a Cu2+ ion to give [CuCl4]2-.
• The name shows the 4 (tetra) chlorines
(chloro) around a copper in an overall
negative ion (cuprate).
• The copper has on oxidation state of +2.
This is the tetrachlorocuprate(II) ion and
each Cl has a -1 charge, so overall charge
of the ion is -2.
• [Al(H2O)2(OH)4]- is called the
diaquatetrahydroxoaluminate ion.
• Break the name into pieces so that you can see
exactly what refers to what. Don't forget that the
two different ligands are named in alphabetical
order - aqua before hydroxo - ignoring the
prefixes, di and tetra.
• The oxidation state of the aluminum could be
shown, but isn't absolutely necessary because
aluminum only has the one oxidation state in its
compounds.
• The full name is the
diaquatetrahydroxoaluminate(III) ion.
THE SHAPES OF COMPLEX
METAL IONS
• These shapes are for complex ions formed
using monodentate ligands - ligands which
only form one bond to the central metal
ion.
• Octahedral – coordination # = 6
• Linear - coordination # = 2
• Tetrahedral – coordination # = 4
• Square planar – coordination # = 4
6-co-ordinated complex ions
• These are complex ions in which the
central metal ion is forming six bonds to
six ligands.
• These ions have an octahedral shape.
• Four of the ligands are in one plane, with
the fifth one above the plane, and the sixth
one below the plane.
4-co-ordinated complex ions
• These are far less common, and they can
take up one of two different shapes.
• Tetrahedral ions
• [CuCl4]2- and [CoCl4]2-.
• The copper(II) and cobalt(II) ions have four
chloride ions bonded to them rather than
six, because the chloride ions are too big
to fit any more around the central metal
ion.
Tetrahedral ions
4-co-ordinated complex ions
• A square planar complex
• Occasionally a 4-co-ordinated complex
turns out to be square planar.
• There's no easy way of predicting that this
is going to happen.
• The only one you might possibly come
across at this level is cisplatin which is
used as an anti-cancer drug.
Cisplatin is a neutral complex, Pt(NH3)2Cl2. It
is neutral because the 2+ charge of the
original platinum(II) ion is exactly cancelled
by the two negative charges supplied by the
chloride ions.
Geometric isomerism
Geometric isomerism
• The two structures are isomers because there is no
way that you can just twist one to turn it into the other.
The complexes are both locked into their current
forms.
• The terms cis and trans are used in the same way as
they are in organic chemistry.
• Trans implies "opposite" or “across” - notice that the
ammonias are arranged opposite each other in that
version, and so are the chlorines.
• Cis implies "on the same side" - in this instance, that
just means that the ammonias and the chlorines are
adjacent to each other.
• Cis-trans isomerism occurs in octahedral and square
planar complexes (but not tetrahedral).
WRITING EQUATIONS
• Excess ammonia is added to a solution of
zinc nitrate.
• Zn2+ + NH3 [Zn(NH3)6]2+
• 2005 AP Exam
WRITING EQUATIONS
• Excess hydrochloric acid is added to a
solution of nickel(II) nitrate.
• NI2+ + Cl- [NiCl4]2-
• 2006 AP test
