Nomenclature of Coordination

Complexes
Coordination complexes have their own classes of isomers, different magnetic properties andcolors, and various
applications (photography, cancer treatment, etc), so it makes sense that they would have a naming system as well.
Consisting of a metal and ligands, their formulas follow the pattern [Metal Anions Neutrals] Charge, while names are
written Prefix Ligands Metal(Oxidation State).

Introduction
According to the Lewis base theory, ligands are Lewis bases since they can donate electrons to the central metal
atom. The metals, in turn, are Lewis acids since they accept electrons. Coordination complexes consist of a ligand
and a metal center cation. The overall charge can be positive, negative, or neutral. Coordination compounds are
complex or contain complex ions, for example:

Complex Cation: [CO(NH3)6]3+

Complex Anion: [CoCl4(NH3)2]

Neutral Complex: [CoCl3(NH3)3]

Coordination Compound: K4[Fe(CN)6]

A ligand can be an anion or a neutral molecule that donates an electron pair to the complex. Ex: NH3, H2O, Cl-. The
number of ligands that attach to a metal depends on whether the ligand is monodentate, bidentate, or polydentate.
For more information, see Ligands andChelation.

Naming Coordination Complexes

Given Formula Write Name
To begin naming coordination complexes, here are some things to keep in mind.
1.
2.
3.

Ligands are named first in alphabetical order.

The name of the metal comes next.
The oxidation state of the metal follows, noted by a Roman numeral in parentheses (II, IV).

Rules for Naming the Ligands

1. Ligands that act as anions which end in "-ide" are replaced with an ending "-o" (e.g., Chloride Chloro).
Anions ending with "-ite" and "-ate" are replaced with endings "-ito" and "-ato" respectively (e.g., Nitrite Nitrito,
Nitrate Nitrato).

Anionic Monodentate Ligands

F-

Fluoro

OH-

Hydroxo

Cl-

Chloro

SO42-

Sulfato

Br-

Bromo

S2O32-

Thiosulfato

I-

Iodo

NO2-

Nitrito-N-; Nitro

O2-

Oxo

ONO-

Nitrito-O-; Nitrito

CN-

Cyano

SCN-

Thiocyanato-S-; Thiocyanato

NC-

Isocyano

NCS-

Thiocyanato-N-; Isothiocyanato

2. Most neutral molecules that are ligands carry their normal name. The few exceptions are the first four on the chart:
ammine, aqua, carbonyl, and nitrosyl.

Neutral Monodentate Ligands

NH3

Ammine

H2O

Aqua

CO

Carbonyl

NO

Nitrosyl

CH3NH2

Methylamine

C5H5N

Pyridine

(Note: Ammine is spelled with two m's when referring to a ligand. Amines are something else.)
Polydentate ligands follow the same rules for anions and neutral molecules.

en

Ethylenediamine

ox2-

Oxalato

EDTA4-

Ethylenediaminetetraacetato

3. The number of ligands present in the complex is indicated with the prefixes di, tri, etc. The exceptions are
polydentates that have a prefix already in their name (en and EDTA4- are the most common). When indicating how
many of these are present in a coordination complex, put the ligand's name in parentheses and use bis, tris,
and tetrakis.

Normal

Polydentates

mono

di

bis

tri

tris

tetra

tetrakis

penta

hexa

Example 1
What is the name oft his complex ion: [CrCl2(H2O)4]+ ?
SOLUTION

Let's start by identifying the ligands. The ligands here are Cl and H 2O. Therefore, we will use the monodentate ligand names of "chloro" and "aqu
Alphabetically, aqua comes before chloro, so this will be their order in the complex's name. There are 4 aqua's and 2 chloro's, so we will add t
number prefixes before the names. Since both are monodentate ligands, we will say "tetra[aqua]di[chloro]". Now that the ligands are named, we w
name the metal itself. The metal is Cr, which is chromium. Therefore, this coordination complex is called tetraaquadichlorochromium(III) ion. <-S
the next section for an explanation of the (III).

Prefixes always go before the ligand name; they are not taken into account when putting ligands in alphabetical order.
Note
that
"mono"
often
is
not
used.
For
example,
[FeCl(CO)2(NH3)3]2+ would
be
called
triamminechlorodicarbonyliron(III) ion. Remember that ligands are always named first, before the metal is.

Example 2
What is the name oft his complex ion: [CoCl2(en)2]+?
SOLUTION
We take the same approach. There are two chloro and ethylenediamine ligands. The metal is Co, cobalt. We follow the same steps, except that en is a
polydentate ligand with a prefix in its name (ethylenediamine), so "bis" is used instead of "bi", and parentheses are added. Therefore, this coordination
complex is called dichlorobis(ethylenediamine)cobalt(III) ion.

Rules for Naming the Metal Center and

Oxidation State
When naming the metal center, you must know the formal metal name and the oxidation state. To show the oxidation
state, we use Roman numerals inside parenthesis. For example, in the problems above, chromium and cobalt have
the oxidation state of +3, so that is why they have (III) after them. Copper, with an oxidation state of +2 , is denoted as
copper(II). If the overall coordination complex is an anion, the ending "-ate" is attached to the metal center. Some
metals also change to their Latin names in this situation. Copper +2 will change into cuprate(II). The following change
to their Latin names when part of an anion complex:

Transition Metal

Latin

Iron

Ferrate

Copper

Cuprate

Tin

Stannate

Silver

Argentate

Lead

Plumbate

Gold

Aurate

The rest of the metals simply have -ate added to the end (cobaltate, nickelate, zincate, osmate, cadmate, platinate,
mercurate, etc. Note that the -ate tends to replace -um or -ium, if present).
Finally, when a complex has an overall charge, "ion" is written after it. This is not necessary if it is neutral or part of a
coordination compound (see EX 3). Here are some examples with determining oxidation states, naming a metal in an
anion complex, and naming coordination compounds.

Example 3
What is the name of [Cr(OH)4]- ?
SOLUTION
Immediately we know that this complex is an anion. There is only one monodentate ligand, hydroxide. There are four of them, so we will use the
name "tetrahydroxo". The metal is chromium, but since the complex is an anion, we will have to use the "-ate" ending, yielding "chromate". The
oxidation state of the metal is 3 (hint: x+(-1)4=-1). Write this with Roman numerals and parentheses (III) and place it after the metal to get
tetrahydroxochromate(III) ion.

Example 4
What is the name of [CuCl4]2- ?
SOLUTION
If you got tetrachlorocuprate(II) ion, you are correct.

A last little side note: when naming a coordination compound, it is important that you name the cation first, then the
anion. You base this on the charge of the ligand. Think of NaCl. Na, the positive cation, comes first and Cl, the
negative anion, follows.

Examples 5
What is the name of [Pt(NH3)4)][Pt(Cl)4] ?
SOLUTION

NH3 is neutral, making the first complex positively charged overall. Cl has a -1 charge, making the second complex the anion. Therefore, you w
write the complex with NH3 first, followed by the one with Cl (the same order as the formula). This coordination compound is calle

tetraammineplatinum(II) tetrachloroplatinate(II).
Distinguishing between linkage isomers:

Examples 6
What is the name of [CoCl(NO2)(NH3)4]+ ?
SOLUTION

This coordination complex is called tetraamminechloronitrito-N-cobalt(III). N comes before the O in the symbol for the nitrite ligand, so it is calle
nitrito-N. If an O came first, as in [CoCl(ONO)(NH3)4]+, the ligand would be called nitrito-O, yielding the name tetraamminechloronitrito-O
cobalt(III). Nitro (for NO2) and nitrito (for ONO) can also be used to describe the nitrite ligand, yielding the names tetraamminechloronitrocobalt(II
and tetraamminechloronitritocobalt(III).

Writing Formulas of Coordination

Complexes
The formula of a coordination complex is written in a different order than its name. The chemical symbol of the metal
center is written first. The ligands are written next, with anion ligands coming before neutral ligands. If there is more
than one anion or neutral ligand, they are written in alphabetical order according to the first letter in their chemical
formula.

In a coordination compound's name, when one of the ions is just an element, the number of atoms is not indicated
with a prefix. Since it still has to be written in the formula, it is determined by balancing the overall charge of the
compound. (For example, tetrafluorochromium(VI) chloride becomes [CrF4]Cl2. See EX4 for practice.)
Here are some examples:

Examples

EX1: Amminetetraaquachromium(II) ion would be written as [Cr(H 2O)4(NH3)]+2. Both ligands are neutral, so they are ordered
alphabetically with H2O before NH3. (Their order in the formula is the opposite of that in the complex's name since one uses their
chemical symbols and the other uses the names of the ligands.)
EX2: Amminesulfatochromium(II) is written as [Cr(SO4)(NH3)]. SO4 is an anion, so it comes before NH3.
EX3: Amminetetraaquachromium(II) sulfate -> Try this on your own. Did you get [Cr(H2O)4(NH3)]SO4? If you did, you are correct.
EX4: Potassium hexacyanoferrate(III) -> Try this on your own. Did you get K3[Fe(CN)6]? Remember to balance the K!