Ch 21.

Nonmetals, Metalloids,
Metals, and Metal Complexes

Brady & Senese, 5th Ed.

Index
• 21.1 Nonmetals and metalloids are found as free elements and in
compounds
• 21.2 Nonmetallic elements in their free states have structures of
varying complexity
• 21.3 Metals are prepared from compounds by reduction
• 21.4 Metallurgy is the science and technology of metals
• 21.5 Complex ions are formed by many metals
• 21.6 The nomenclature of metal complexes follows an extension of
the rules developed earlier
• 21.7 Coordination number and structure are often related
• 21.8 Isomers of coordination complexes are compounds with the same
formula but different structures
• 21.9 Bonding in transition metal complexes involves d orbitals
• 21.10 Metal ions serve critical functions in biological systems

2
Figure 21.1

Metals

21.1 Nonmetals and metalloids are found as free elements and in compounds 3
Preparation of Nonmetals

• Occur both as free elements or in molecular

forms
• Except for He and Rn, noble gases are obtained
from air
 He is a radioactive decay product found in gaseous
deposits beneath the earth
 Rn is radioactive and a decay product, only found in
minute quantities in nature
• Noble gases are elemental from air

21.1 Nonmetals and metalloids are found as free elements and in compounds 4
Recovery
May be recovered from the anion form using:
• a single replacement type reaction
 2NaCl + F2 →2NaF + Cl2
 Activity: F2>Cl2>Br2>I2
• reaction with an oxidizing agent
2X   MnO 2  4H   X 2  Mn 2  2H 2O
where X  Cl, Br, or I

21.1 Nonmetals and metalloids are found as free elements and in compounds 5
Recovery (con.)

• May be recovered from a compound in which it has a

(+) oxidation state by reaction with a reducing agent
 Ca3(PO4)2(s) + 3 SiO2(s) + 5C(s) →3CaSiO3(l) + 5CO(g) + 2P(g)
• May be recovered using electrolysis of molten
compounds
 2NaCl 2Na + Cl2

21.1 Nonmetals and metalloids are found as free elements and in compounds 6
Your Turn!

Mg3N2(s) + Cl2(g) →
A. MgCl2(s)
B. NCl(g)
C. NR

21.1 Nonmetals and metalloids are found as free elements and in compounds 7
Metalloids

• In most of their compounds, are combined with

nonmetals, either in a molecular structure or in an
oxoanion
• Have lower electronegativities than nonmetals, so
the metalloids exists in a positive oxidation state

21.1 Nonmetals and metalloids are found as free elements and in compounds 8
Preparation of Metalloids

• Obtained by chemical reduction, accomplished

with either hydrogen or carbon as the reducing
agent

2BCl 3 (g)  3H 2 (g)  2B(s)  6HCl(g)

SiO 2 (s)  C(s)  Si(s)  CO2 (g)
GeO 2 (s)  2H 2 (g)  Ge(s)  2H 2O(g)

21.1 Nonmetals and metalloids are found as free elements and in compounds 9
Your Turn!

QmOn(s) + C(gr) → ? If Q is a semimetal

A. QkCl
B. Q
C. Not enough information

21.1 Nonmetals and metalloids are found as free elements and in compounds 10
Bonding In The Nonmetallic Elements
Except the noble gases, exist in nature with
covalent bonds involving p orbitals:
• period 2 elements form multiple bonds easily: C
in graphite, and N2 and O2 exhibit multiple bonds
• period 3, 4, 5, and 6 tend to prefer single bonds
• Group VIIA all exist as diatomic molecules
because only a single bond is required

21.2 Nonmetallic elements in their free states have structures of varying complexity 11
Allotropy
• Elements may exist in more than one form
(allotropes), due to:
 differences in molecular structure
 differences in the packing of molecules in the solid

21.2 Nonmetallic elements in their free states have structures of varying complexity 12
Boron

• B has 3 valence electrons

• It is found in a B12 cluster covalent solid

21.2 Nonmetallic elements in their free states have structures of varying complexity 13
 Elements of Group VIA
• O has two allotropes: O2 and O3 (ozone)

• Se is below S and also forms eight-member rings

• Se and Te can be found as long chains

21.2 Nonmetallic elements in their free states have structures of varying complexity 14
Elements Of Group VA
• Need three electrons to achieve a noble gas
configuration
• Phosphorus is found as three allotropes: P4(white),
P10(red), and Pblack
• Arsenic and antimony, form As4 and Sb4 molecules
 their more stable forms have a metallic appearance and a
structure more like black phosphorus

21.2 Nonmetallic elements in their free states have structures of varying complexity 15
Your Turn!

The structure of molecular elements has a great deal

to do with their reactivity. High strain in the bond
angles causes them to react more violently than
other elements. Which of the following will react
more strongly with water?

A. B. C.

21.2 Nonmetallic elements in their free states have structures of varying complexity 16
Sources Of Metals
• Metals are found in seawater and in mineral
deposits
• To reclaim these metals
 use electrolysis (especially for active metals)
 NaCl(l) Na + Cl2
 pass them over reducing agents such as carbon
 2PbO + C 2Pb + CO2
 use single replacement reactions
 2Ag+ + Cu→Cu2+ + 2Ag
 recover them from some compounds by heating them
strongly
 2HgO 2Hg + O2

21.3 Metals are prepared from compounds by reduction 17

Predicting the Temperature at which
Thermal Decomposition Occurs
• Write the equation showing the decomposition
 MxOy(s) → xM(s) + y/2 O2(g)
• This reaction is spontaneous when ΔG<0,
• The temperature at which it is at equilibrium,
Tc, is  
Tc  
S

• We must exceed this temperature for reactions

in which ΔH° and ΔS° are both (+) [true for
most metal oxides]

21.3 Metals are prepared from compounds by reduction 18

Learning Check:

• Write the equation that accompanies the thermal

decomposition of the following:
 ZnO •2ZnO(s)→2Zn(s) + O2(g)
• At what temperature will ZnO undergo thermal
decomposition?
  348.3 kJ/mol
Tc 
S
; Tc 
0.201 kJ/molK
 1.73(103) •At all temperatures
ΔHf ° Sf° ΔGf,298 °
O2(g) 0 205 0
Zn(s) 0 41.6 0
ZnO(s) −348.3 43.6 −318.3

21.3 Metals are prepared from compounds by reduction 19

Learning Check:

• Write the equation that accompanies the thermal

decomposition of the following:
 CaO •2CaO(s)→2Ca(s) + O2(g)
• At what temperature will CaO undergo thermal
decomposition?
  635.5 kJ/mol
Tc  ; Tc   3.1(103) •At all temperatures
S 0.2082 kJ/molK
ΔHf ° Sf° ΔGf,298 °
CaO(s) −635.5 40 −604.2
O2(g) 0 205 0
Ca(s) 0 41.6 0

21.3 Metals are prepared from compounds by reduction 20

Your Turn!

MgO(s) →Mg(s) + 1/2 O2(g)

What is the temperature at which the decomposition
will occur?
A. > -22.3 ºC
B. > -2.23(10-4) K >-2.23(104) K
C. > -22.3 K
D. None of these ∆Hº ∆Gº Sº
kJ/mol kJ/mol J/molK
Mg(s) 0 0 32.69
O2(g) 0 0 41.6
MgO(s) -601.2 -569 26.9
21.3 Metals are prepared from compounds by reduction 21
How Do We Recover Metals? (Metallurgy)
1. Concentration. Reduce the
impurities (gangue), and convert
some metal compounds into
substances that can be more easily
reduced
 Ex. flotation, washing, sieving
 Roasting to convert to oxides
2. Reduction. Convert the metal
compound to the metal
3. Refining. Remove impurities and
adjust the composition of the metal
(alloys formed)
21.4 Metallurgy is the science and technology of metals 22
Blast Furnaces

• Iron oxide is burned in high

temperature with a charge of
limestone and coke (Coal)
• Then burned with a reducing
agent (CO)
• Pig iron is drawn from the
bottom with some impurities
(slag)

21.4 Metallurgy is the science and technology of metals 23

Complex Ions (Coordination Complexes)

• Form through Lewis acid/base reactions

• Metal acts as a Lewis acid
• Ligand acts as Lewis base to form coordinate
covalent bond

21.5 Complex ions are formed by many metals 24

Common Ligands
• Anions
 F−, Cl−, Br−, I−, S2−, NO2−, CN−,
OH−, SCN− S2O32−
• Molecules
 H2O, NH3
• Chelating agents (polydentate
ligands)
 edta, en, C2O42-
 create much more stable complex
ions (smaller Kinst) than other
complex ions.

21.5 Complex ions are formed by many metals 25

Formulas Of Complex Ions

1. The symbol for the metal ion is always given first,

followed by the ligands
2. The charge on the complex is the algebraic sum of
the charge on the metal ion and the charges on the
ligands

21.5 Complex ions are formed by many metals 26

Learning Check

• What is the formula for the complex made by Cu2+

and four ammonia molecules?
• [Cu(NH3)4]2+
• What is the formula for the complex formed by
Ag+ and two cyanide ions?
• [Ag(CN)2]-

21.5 Complex ions are formed by many metals 27

Your Turn

What is the formula of the complex ion made by

Aluminum ion with 6 fluoride ions?
A. [AlF6]3+
B. [AlF6]-
C. [AlF6]3-
D. None of these

21.5 Complex ions are formed by many metals 28

Naming Complex Ions

1. Cationic species are named before anionic

species
ex: [Al(OH)4]- aluminum is named before the OH-
2. Names of anionic ligands always end in the
suffix -o (ligands whose names end in -ite
or -ate become -ito and -ato, respectively)

21.6 The nomenclature of metal complexes follows an extension of the rules developed 29
earlier
Learning Check

What should the following be called if part of a

complex ion?
• Cl- •chloro
• OH- •hydroxo-
• CN- •cyano-
• C2O42- •oxalato-

21.6 The nomenclature of metal complexes follows an extension of the rules developed 30
earlier
Nomenclature (Cont.)

3. Neutral ligands are given the same name as

the neutral molecule:
 exceptions to this, however, are water (aqua) and
ammonia (ammine)
4. When there is more than one of a particular
ligand, their number is specified by the
Greek prefixes (di- = 2, tri- = 3, etc…),
 when confusion might result, the following are used
instead: bis = 2, tris = 3, tetrakis = 4

21.6 The nomenclature of metal complexes follows an extension of the rules developed 31
earlier
Learning Check

• dba is a ligand called dibenzylideneacetone. If

two if them are used, as in Pd(dba)2, what prefix
should we use?
• bis-
• PPh3 is a ligand called triphenylphosphine. If four
of them are used, what prefix should we use?
• tetrakis-

21.6 The nomenclature of metal complexes follows an extension of the rules developed 32
earlier
Nomenclature (Cont.)

5. In the formula of a complex, the symbol

for the metal is written first, followed by
those of the ligands
 anionic ligands are written first (in alphabetical
order), followed by neutral ligands (also in
alphabetical order).
 alphabetize according to the first letter of the name
of the ligand, not the first letter of the prefix

21.6 The nomenclature of metal complexes follows an extension of the rules developed 33
earlier
Learning Check: What are the formulas?

• Molybdenum(II) forms a complex ion with 4

hydrogen arsenate ions, HAsO42- and 2 Mo2+
ions
• [Mo2(HAsO4)4]2–
• Rh3+ forms a complex ion with 4 neutral pyridine
(py) molecules and 2 chloride ions
• [RhCl2(py)4 ] +
• V4+ forms a complex with 2 oxalate ions (OX2-),
and 1 oxide ion (O2-)
• [V(Ox)2O]2-
21.6 The nomenclature of metal complexes follows an extension of the rules developed 34
earlier
Your Turn!

Arrange the following ligands in terms of the order

in which they would occur in a complex ion
formula: NH3, Cl-, OH-, en
A. Cl-, en, NH3, OH-
B. NH3, Cl-, en, OH-
C. en, NH3, Cl-, OH-
D. Cl-, OH-, NH3, en

21.6 The nomenclature of metal complexes follows an extension of the rules developed 35
earlier
Nomenclature

6. In the name of the complex, the ligands are

named first, in alphabetical order without
regard to charge, followed by the name of
the metal
 The oxidation state of the metal in the complex is written in
Roman numerals within parentheses following the name of
the metal

21.6 The nomenclature of metal complexes follows an extension of the rules developed 36
earlier
Learning Check

To avoid confusion, how should each be named?

• [Co(CO3)(C2H6N2)4] + cation contains 2 ligands:
neutral acetamidine, and the negative carbonate
ion
• tetrakis(acetamidine)carbonatocobalt(III)
• [Ni(3,4-dimethylpyradine)4]2+ cation has 1 ligand,
neutral 3,4-dimethylpyridine
• tetrakis-(3,4-dimethylpyridine)nickel(II)

21.6 The nomenclature of metal complexes follows an extension of the rules developed 37
earlier
Nomenclature (Cont.)

7. Negative (anionic) complex ions always end in

the suffix –ate: this suffix is appended to the
English name of the metal atom in most cases
 if the name of the metal ends in -ium, -um or -ese, the
suffix is replaced by -ate.
 for metals whose symbols are derived from their Latin
names, the suffix -ate is appended to the Latin stem.
(An exception, however, is mercury; in an anion it is
named mercurate)

21.6 The nomenclature of metal complexes follows an extension of the rules developed 38
earlier
Nomenclature (Cont.)

8. For neutral or positively charged complexes, the

metal is always specified with the English name
for the element, without any suffix.
9. The oxidation state of the metal in the complex is
written in Roman numerals within parentheses
following the name of the metal

21.6 The nomenclature of metal complexes follows an extension of the rules developed 39
earlier
Learning Check: Name the Following:

• [Ag(CN)2]-
• dicyanoargentate ion
• [Zn(OH)4] 2-
• tetrahydroxozincate ion
• [Cu(NH3)4] 2+
• tetraamminecopper(II) ion
• [Mn(en)3] 2+
• triethylenediaminemanganese(II) ion

21.6 The nomenclature of metal complexes follows an extension of the rules developed 40
earlier
Learning Check
Predict the formula from the following names:
• tetracyanocuprate(I) ion
• [Cu(CN)4]3-
• triamminethiocyanoplatinum(III) ion
• [PtSCN(NH3)3]2+
• diamminetetraaquacopper(II) ion
• [Cu(NH3)2(H2O)4]2+
• hexaamminecobalt(III) ion
• [Co(NH3)6]3+

21.6 The nomenclature of metal complexes follows an extension of the rules 41

developed earlier
Coordination Numbers (C.N.)

• In complex ions, the metals form coordinate

covalent bonds with other substances
• The C.N. tells us how many donor atoms are
attached to the metal
• Monodentate ligands each have one donor atom,
bidentate ligands have two donor atoms, and so
forth
• Often, the geometry of the complex ion helps us to
identify the C.N.

21.7 Coordination number and structure are often related 42

Your Turn!

Which is the correct name for [Au(CN)2]-

A. goldcyanide ion
B. gold(I)dicyano ion
C. dicyanoaurate ion
D. dicyanoaurate(I) ion

21.7 Coordination number and structure are often related 43

CN Geometry Compounds

2 linear [H3N-Ag-NH3]+

4 A tetrahedral geometry is usually found

with metal ions that have completely
filled d subshells such as Zn
e.g. [Zn(OH)4]2-

Square planar geometries are observed

for complexes of Cu2+, Ni2+, and
especially Pt2+.

21.7 Coordination number and structure are often related 44

CN Geometry Compounds

6 [Ni(H2O)6]2+

21.7 Coordination number and structure are often related 45

Your Turn

Which is the likely geometry of [AlF6]3-

A. linear
B. tetrahedral
C. octahedral
D. trigonal bipyramidal

21.7 Coordination number and structure are often related 46

Coordination Isomers

• When two complex ions have the same formula,

they may not have the same arrangement of atoms
• Some are attached coordinately, while others may
be attracted electrically
• Water may be attached as a ligand, or trapped
within the crystal as a water of hydration
 [Cr(H2O)6]Cl3 purple
 CrCl(H2O)5Cl2·H2O blue-green
 [CrCl2(H2O)4]Cl·2H2O green

21.8 Isomers of coordination complexes are compounds with the same formula but 47
different structures
Stereoisomers

• Have the same atoms attached in the same way,

but arranged differently.
• Occur for square planar and octahedral complex
ions.

21.8 Isomers of coordination complexes are compounds with the same formula but 48
different structures
Optical Isomers

• Differ in their “handedness”; they are mirror

images of one another, and have unique properties
• Are non-superimposable

21.8 Isomers of coordination complexes are compounds with the same formula but 49
different structures
Properties of Transition Metals

• They are usually colored, whereas complexes of

the representative metals are usually colorless, and
• Their magnetic properties are often affected by the
ligands attached to the metal ion
 this is due to the interaction of d orbitals with the
ligands, explained by Crystal Field Theory

21.9 Bonding in transition metal complexes involves d orbitals 50

Crystal Field Theory

• The d orbitals are

degenerate (same
energy) when isolated
• When ligands are
attached, they interact
with the electrical
fields of the d orbitals
differently because the
electrons are situated
differently in each
orbital
21.9 Bonding in transition metal complexes involves d orbitals 51
Ligands in an Octahedral Complex

• Affect 3 of the d orbitals similarly

• Two of the d orbitals are repelled to a greater
extent.
• The difference in energy is terms crystal field
splitting, and is symbolized Δ

21.9 Bonding in transition metal complexes involves d orbitals 52

Factors Affecting the Magnitude of Δ
• The nature of the ligand: some ligands produce a larger
splitting of the energies of the d orbitals than others

• The oxidation state of the metal: for a given metal and

ligand, the size of Δ increases with an increase in the
oxidation number of the metal
• The period in which the metal occurs:
for a given ligand and oxidation state, the size of Δ
increases going down a group

21.9 Bonding in transition metal complexes involves d orbitals 53

Your Turn!

Which of the following complexes is likely to have

the greatest ∆?
A. [Cu(NH3)2] +
B. [CuCl2]-
C. [Cu(CN)2]-
D. All are the same

21.9 Bonding in transition metal complexes involves d orbitals 54

Uses for Δ
• Prediction of ion stability
 as oxidation state increases,
the ion contracts. repulsions
increase
• Explanation of color
variations
 electrons may move between
d orbitals.
• Explanation of magnetic
properties
 If Δ>P, pairs in lower level
 If P> Δ, remains unpaired.

21.9 Bonding in transition metal complexes involves d orbitals 55

Δ In Other Geometries

Note that field

splitting is different
when ligands are
arranged differently

21.9 Bonding in transition metal complexes involves d orbitals 56

Some Examples of Body Functions and Their
Corresponding Essential Metals in the Human Body
Body Function Metal
Blood pressure and blood coagulation Na, Ca
Oxygen transport and storage Fe
Teeth and bone structure Ca
Urinary stone formation Ca
Control of pH in blood Zn
Muscle contraction Ca, Mg
Maintenance of stomach acidity K
Respiration Fe, Cu
Cell division Ca, Fe, Co

21.10 Metal ions serve critical functions in biological systems 57

Hemoglobin And Vitamin B12

21.10 Metal ions serve critical functions in biological systems 58