Homework in Chemistry 3 SELF-LEARNING ACTIVITY ON Fourth Quarter

(Science Option/Elective) COORDINATION COMPOUNDS SY 2018-2019

Transition metals have a distinct tendency to form complex ions. A coordination compound typically consists of a
complex ion and counter ion. Our understanding of the nature of coordination compounds stems from the classic
work of Alfred Werner, who prepared and characterized many coordination compounds. In 1893, at the age of 26,
Werner proposed what is now commonly referred to as Werner’s coordination theory.

Nineteenth-century chemists were puzzled by a certain class of reactions that seemed to violate valence theory. For
example, the valences of the elements in cobalt (III) chloride and in ammonia seem to be completely satisfied, and
yet these two substances react to form a stable compound having the formula CoCl3 · 6 NH3. To explain this behavior,
Werner postulated that most elements exhibit two types of valence: primary valence and secondary valence. In
modern terminology, primary valence corresponds to the oxidation number and secondary valence to the
coordination number of the element. In CoCl3 · 6 NH3, according to Werner, cobalt has a primary valence of 3 and a
secondary valence of 6.

Today we use the formula [Co(NH3)6]Cl3 to indicate that the ammonia molecules and the cobalt atom form a complex
ion; the chloride ions are not part of the complex but are held to it by ionic forces. Most, but not all, of the metals in
coordination compounds are transition metals. The molecules or ions that surround the metal in a complex ion are
called ligands. The interactions between a metal atom and the ligands can be thought of as Lewis acid-base reactions.
As we know, a Lewis base is a substance capable of donating one or more electron pairs. Ligands act as Lewis bases
by donating electrons to metals, which act as Lewis acids. A transition metal atom (in either its neutral or positively
charged state) acts as a Lewis acid, accepting (and sharing) pairs of electrons from the Lewis bases. Thus, the metal-
ligand bonds are usually coordinate covalent bonds

The atom in a ligand that is bound directly to the metal atom is known as the donor atom. For example, nitrogen is
the donor atom in the [Cu(NH3)4]2+ complex ion. The coordination number in coordination compounds is defined
as the number of donor atoms surrounding the central metal atom in a complex ion. For example, the coordination
number of Ag+ in [Ag(NH3)2]+ is 2, that of Cu2+ in [Cu(NH3)4]2+ is 4, and that of Fe3+ in [Fe(CN)6]3+ is 6. The most
common coordination numbers are 4 and 6, but coordination numbers such as 2 and 5 are also known. Depending
on the number of donor atoms present, ligands are classified as monodentate, bidentate, or polydentate (see Table
1). H2O and NH3 are monodentate ligands with only one donor atom each. One bidentate ligand is ethylenediamine
(sometimes abbreviated “en”; see Table 1).

Bidentate and polydentate ligands are also called chelating agents because of their ability to hold the metal atom like
a claw (from the Greek chele, meaning “claw”). One example is ethylenediaminetetraacetate ion (EDTA), a
polydentate ligand used to treat metal poisoning. Six donor atoms enable EDTA to form a very stable complex ion
with lead. In this form, it is removed from the blood and tissues and excreted from the body. EDTA is also used to
clean up spills of radioactive metals.
Figure 1. (a) Structure of a metal-ethylenediamine complex cation, such as [Co(en)3]2+. Each ethylenediamine molecule
provides two N donor atoms and is therefore a bidentate ligand. (b) Simplified structure of the same complex cation.

Table 1. Some Common Ligands

Note:

OXIDATION NUMBERS OF METALS IN COORDINATION COMPOUNDS

Another important property of coordination compounds is the oxidation number of the central metal atom. The net
charge of a complex ion is the sum of the charges on the central metal atom and its surrounding ligands. In the
[PtCl6]2- ion, for example, each chloride ion has an oxidation number of -1, so the oxidation number of Pt must be +4.
If the ligands do not bear net charges, the oxidation number of the metal is equal to the charge of the complex ion.
Thus, in [Cu(NH3)4]2+ each NH3 is neutral, so the oxidation number of Cu is +2.
Example 1: Specify the oxidation number of the central metal atom in each of the following compounds:
(a) [Ru(NH3)5(H2O)]Cl2, (b) [Cr(NH3)6](NO3)3, (c) [Fe(CO)5], and (d) K4[Fe(CN)6].

Strategy The oxidation number of the metal atom is equal to its charge. First, we examine the anion or the cation
that electrically balances the complex ion. This step gives us the net charge of the complex ion. Next, from the nature
of the ligands (charged or neutral species) we can deduce the net charge of the metal and hence its oxidation number.

Solution
(a) Both NH3 and H2O are neutral species. Because each chloride ion carries a -1 charge, and there are two Cl⁻ ions,
the oxidation number of Ru must be +2.
(b) Each nitrate ion has a charge of -1; therefore, the cation must be [Cr(NH3)6]3+. NH3 is neutral, so the oxidation
number of Cr is +3.
(c) Because the CO species are neutral, the oxidation number of Fe is zero.
(d) Each potassium ion has a charge of +1; therefore, the anion is [Fe(CN)6]4-. Next, we know that each cyanide group
bears a charge of -1, so Fe must have an oxidation number of +2.

NAMING COORDINATION COMPOUNDS

Now that we have discussed the various types of ligands and the oxidation numbers of metals, our next step is to
learn what to call these coordination compounds. The rules for naming coordination compounds are as follows:
1) The cation is named before the anion, as in other ionic compounds. The rule holds regardless of whether the
complex ion bears a net positive or a negative charge. For example, in K3[Fe(CN)6] and [Co(NH3)4Cl2]Cl
compound, we name the K+ and [Co(NH3)4Cl2]+ cations first, respectively.
2) Within a complex ion the ligands are named first, in alphabetical order, and the metal ion is named last.
3) The names of anionic ligands end with the letter o, whereas a neutral ligand is usually called by the name of
the molecule. The exceptions are H2O (aqua), CO (carbonyl), and NH3 (ammine).
4) When several ligands of a particular kind are present, we use the Greek prefixes di-, tri-, tetra-, penta-, and
hexa- to name them. Thus, the ligands in the cation [Co(NH3)4Cl2]+ are “tetraamminedichloro.” (Note that
prefixes are ignored when alphabetizing ligands.) If the ligand itself contains a Greek prefix, we use the
prefixes bis (2), tris (3), and tetrakis (4) to indicate the number of ligands present. For example, the ligand
ethylenediamine already contains di; therefore, if two such ligands are present the name is
bis(ethylenediamine).
5) The oxidation number of the metal is written in Roman numerals following the name of the metal. For
example, the Roman numeral III is used to indicate the +3 oxidation state of chromium in [Cr(NH3)4Cl2]+,
which is called tetraamminedichlorochromium( III) ion.
6) If the complex is an anion, its name ends in -ate. For example, in K4[Fe(CN)6] the anion [Fe(CN)6]4- is called
hexacyanoferrate(II) ion. Note that the Roman numeral II indicates the oxidation state of iron. See table
below for names of anions containing metal atoms.
 Table 2. Name of Common Ligands in Coordination Compounds Table 3. Names of Anions
Containing Metal Atoms

NOTE:
The Nitrate, NO3, ion is named “nitrato”
The Nitrite, NO2, ion is preferably named “nitrito”

The nitrite and thiocyanate ions are ambidentate ligands, meaning, they can attach to the central metal atom
through either one of its atoms.

 If the nitrite ion (NO2-) is attached through the N atom the designation nitrito-N- is used; if attached through
an O atom nitrito-O-.
 If the thiocyanate ion is attached through the S atom the name thiocyanato-S- is used; if attachment is through
the N atom 1¬NCS2, thiocyanato-N-.

Example 2: Write the systematic names of the following coordination compounds:

Strategy We follow the preceding procedure for naming coordination compounds and refer to the tables shown
previously for names of ligands and anions containing metal atoms.

Solution
(a) The CO ligands are neutral species and therefore the Ni atom bears no net charge. The compound is called
tetracarbonylnickel(0), or more commonly, nickel tetracarbonyl .
(b) The sodium cation has a positive charge; therefore, the complex anion has a negative charge (AuF4⁻). Each
fluoride ion has a negative charge so the oxidation number of gold must be +3 (to give a net negative charge). The
compound is called sodium tetrafluoroaurate(III) .
(c) The complex ion is the anion and it bears three negative charges because each potassium ion bears a +1 charge.
Looking at [Fe(CN)6]3-, we see that the oxidation number of Fe must be +3 because each cyanide ion bears a -1 charge
(-6 total). The compound is potassium hexacyanoferrate(III). This compound is commonly called potassium
ferricyanide.
(d) As we noted earlier, en is the abbreviation for the ligand ethylenediamine. Because there are three chloride ions
each with a -1 charge, the cation is [Cr(en)3]3+. The en ligands are neutral so the oxidation number of Cr must be +3.
Because there are three en groups present and the name of the ligand already contains di (rule 4), the compound is
called tris(ethylenediamine)chromium(III) chloride .
Example 3: Write the formulas for the following compounds: (a) pentaamminechlorocobalt(III) chloride,
(b) dichlorobis(ethylenediamine)platinum(IV) nitrate, (c) sodium hexanitrocobaltate(III).

Strategy We follow the preceding procedure and refer to the tables shown previously for names of ligands and
anions containing metal atoms.

Solution
(a) The complex cation contains five NH3 groups, a Cl⁻ ion, and a Co ion having a +3 oxidation number. The net charge
of the cation must be +2, [Co(NH3)5Cl]2+. Two chloride anions are needed to balance the positive charges.
Therefore, the formula of the compound is [Co(NH3)5Cl]Cl2.
(b) There are two chloride ions (-1 each), two en groups (neutral), and a Pt ion with an oxidation number of +4. The
net charge on the cation must be +2, [Pt(en)2Cl2]2+. Two nitrate ions are needed to balance the +2 charge of the
complex cation. Therefore, the formula of the compound is [Pt(en)2Cl2](NO3)2.
(c) The complex anion contains six nitro groups (-1 each) and a cobalt ion with an oxidation number of +3. The net
charge on the complex anion must be -3, [Co(NO2)6]3-. Three sodium cations are needed to balance the -3 charge of
the complex anion. Therefore, the formula of the compound is Na3[Co(NO2)6].

Exercises:
1) Give the oxidation numbers of the metals in the following species:
a) K3[Fe(CN)6]
b) K3[Cr(C2O4)3]
c) [Ni(CN)4]2-
d) Na2MoO4
e) MgWO4
f) Fe(CO)5

2) What are the systematic names for the following ions and compounds?
a) [Co(NH3)4Cl2]+
b) [Co(en)2Br2]+
c) Cr(NH3)3Cl3
d) [Co(NH3)6]Cl3
e) [cis-Co(en)2Cl2]+
f) [Pt(NH3)5Cl]Cl3
g) [Co(NH3)5Cl]Cl2

3) Write the formulas for each of the following ions and compounds:
a) tetrahydroxozincate(II)
b) pentaaquachlorochromium(III) chloride
c) tetrabromocuprate(II)
d) ethylenediaminetetraacetatoferrate(II)
e) bis(ethylenediamine)dichlorochromium(III)
f) pentacarbonyliron(0)
g) potassium tetracyanocuprate(II)
h) tetraammineaquachlorocobalt(III) chloride

Activity for all Chemistry 3 Classes: Science Option and Science Elective

Prepared by: Reviewed and Edited by:

MARK MERRILL N. MESA GENALYN ALICE R. VILORIA