4 Chapter 1 | Introduction to Inorganic Chemistry

Figure 1.8 The Fullerene C60,

a Fullerene Compound, a Carbon
Nanotube, Graphene, a Carbon
Peapod, and a Polyyne “Wire”
Connecting Platinum Atoms.

addition, numerous other forms of carbon (for example, carbon nanotubes, nanoribbons,
graphene, and carbon wires) have attracted much interest and show potential for applica-
tions in fields as diverse as nanoelectronics, body armor, and drug delivery. Figure 1.8
provides examples of these newer forms of carbon.
The era of sharp dividing lines between subfields in chemistry has long been ­obsolete.
Many of the subjects in this book, such as acid–base chemistry and organometallic reac-
tions, are of vital interest to organic chemists. Other topics such as ­oxidation–reduction
reactions, spectra, and solubility relations interest analytical chemists. Subjects related
to structure determination, spectra, conductivity, and theories of bonding appeal to
physical chemists. Finally, the use of organometallic catalysts provides a connection to
petroleum and polymer chemistry, and coordination compounds such as hemoglobin and
­metal-containing enzymes provide a similar tie to biochemistry. Many inorganic chemists
work with professionals in other fields to apply chemical discoveries to addressing modern
challenges in medicine, energy, the environment, materials science, and other fields. In
brief, modern inorganic chemistry is not a fragmented field of study, but has numerous
interconnections with other fields of science, medicine, technology, and other disciplines.
The remainder of this chapter is devoted to a short history of the origins of inorganic
chemistry and perspective on more recent developments, intended to provide a sense of
connection to the past and to place some aspects of inorganic chemistry within the context
of larger historical events. In later chapters, brief historical context is provided with the
same intention.

1.3 The History of Inorganic Chemistry

Even before alchemy became a subject of study, many chemical reactions were used and
their products applied to daily life. The first metals used were probably gold and copper,
which can be found in the metallic state in nature. Copper can also be readily formed by
the reduction of malachite—basic copper carbonate, Cu2(CO3)(OH)2—in charcoal fires.
Silver, tin, antimony, and lead were also known as early as 3000 bce. Iron appeared in
 1.3 The History of Inorganic Chemistry | 5

classical Greece and in other areas around the Mediterranean Sea by 1500 bce. At about
the same time, colored glasses and ceramic glazes were introduced, largely composed of
silicon dioxide (SiO2, the major component of sand) and other metallic oxides, which had
been melted and allowed to cool to amorphous solids.
Alchemists were active in China, Egypt, and other centers of civilization early in the
first centuries ce. Although much effort went into attempts to “transmute” base metals into
gold, alchemists also described many other chemical reactions and operations. Distillation,
sublimation, crystallization, and other techniques were developed and used in their stud-
ies. Because of the political and social changes of the time, alchemy shifted into the Arab
world and later—about 1000 to 1500 ce—reappeared in Europe. Gunpowder was used in
Chinese fireworks as early as 1150, and alchemy was also widespread in China and India
at that time. Alchemists appeared in art, literature, and science until at least 1600, by which
time chemistry was beginning to take shape as a science. Roger Bacon (1214–1294), recog-
nized as one of the first great experimental scientists, also wrote extensively about alchemy.
By the seventeenth century, the common strong acids—nitric, sulfuric, and hydro-
chloric—were known, and systematic descriptions of common salts and their reactions
were being accumulated. As experimental techniques improved, the quantitative study of
chemical reactions and the properties of gases became more common, atomic and molecu-
lar weights were determined more accurately, and the groundwork was laid for what later
became the periodic table of the elements. By 1869, the concepts of atoms and molecules
were well established, and it was possible for Mendeleev and Meyer to propose different
forms of the periodic table. Figure 1.9 illustrates Mendeleev’s original periodic table.*
The chemical industry, which had been in existence since very early times in the form
of factories for purifying salts and for smelting and refining metals, expanded as methods
for preparing relatively pure materials became common. In 1896, Becquerel discovered
radioactivity, and another area of study was opened. Studies of subatomic particles, spectra,
and electricity led to the atomic theory of Bohr in 1913, which was soon modified by the
quantum mechanics of Schrödinger and Heisenberg in 1926 and 1927.
Inorganic chemistry as a field of study was extremely important during the early years
of the exploration and development of mineral resources. Qualitative analysis methods were

Ti = 50 Zr = 90 ? = 180 FIGURE 1.9 Mendeleev’s 1869

V = 51 Nb = 94 Ta = 182 Periodic Table. Two years later,
Cr = 52 Mo = 96 W = 186 Mendeleev revised his table
Mn = 53 Rh = 104.4 Pt = 197.4 into a form similar to a modern
Fe = 56 Ru = 104.2 Ir = 198 short-form periodic table, with
Ni = Co = 59 Pd = 106.6 Os = 199 eight groups across.
H=1 Cu = 63.4 Ag = 108 Hg = 200
Be = 9.4 Mg = 24 Zn = 65.2 Cd = 112
B = 11 Al = 27.4 ? = 68 Ur = 116 Au = 197?
C = 12 Si = 28 ? = 70 Sn = 118
N = 14 P = 31 As = 75 Sb = 122 Bi = 210?
O = 16 S = 32 Se = 79.4 Te = 128?
F = 19 Cl = 35.5 Br = 80 J = 127
Li = 7 Na = 23 K = 39 Rb = 85.4 Cs = 133 Tl = 204
Ca = 40 Sr = 87.6 Ba = 137 Pb = 207
? = 45 Ce = 92
?Er = 56 La = 94
?Yt = 60 Di = 95
?In = 75.6 Th = 118 ?

*The original table was published in Zeitschrift für Chemie, 1869, 12, 405. It can be found in English translation,
together with a page from the German article, at web.lemoyne.edu/~giunta/mendeleev.html. See M. Laing,
J. Chem. Educ., 2008, 85, 63 for illustrations of Mendeleev’s various versions of the periodic table, including his
handwritten draft of the 1869 table.
6 Chapter 1 | Introduction to Inorganic Chemistry

developed to help identify minerals and, combined with quantitative methods, to assess
their purity and value. As the Industrial Revolution progressed, so did the chemical industry.
By the early twentieth century, plants for the high volume production of ammonia, nitric
acid, sulfuric acid, sodium hydroxide, and many other inorganic chemicals were common.
Early in the twentieth century, Werner and Jørgensen made considerable progress
on understanding the coordination chemistry of transition metals and also discovered a
number of organometallic compounds. Nevertheless, the popularity of inorganic chem-
istry as a field of study gradually declined during most of the first half of the century.
The need for inorganic chemists to work on military projects during World War II rejuve-
nated interest in the field. As work was done on many projects (not least of which was the
Manhattan Project, in which scientists developed the fission bomb), new areas of research
appeared, and new theories were proposed that prompted further experimental work.
A great expansion of inorganic chemistry began in the 1940s, sparked by the enthusiasm
and ideas generated during World War II.
In the 1950s, an earlier method used to describe the spectra of metal ions surrounded
by negatively charged ions in crystals (crystal field theory)1 was extended by the use of
molecular orbital theory2 to develop ligand field theory for use in coordination compounds,
in which metal ions are surrounded by ions or molecules that donate electron pairs. This
theory gave a more complete picture of the bonding in these compounds. The field devel-
oped rapidly as a result of this theoretical framework, availability of new instruments, and
the generally reawakened interest in inorganic chemistry.
In 1955, Ziegler3 and Natta4 discovered organometallic compounds that could cata-
lyze the polymerization of ethylene at lower temperatures and pressures than the common
industrial method at that time. In addition, the polyethylene formed was more likely to be
made up of linear, rather than branched, molecules and, as a consequence, was stronger
and more durable. Other catalysts were soon developed, and their study contributed to the
rapid expansion of organometallic chemistry, still a rapidly growing area.
The study of biological materials containing metal atoms has also progressed rapidly.
The development of new experimental methods allowed more thorough study of these
compounds, and the related theoretical work provided connections to other areas of study.
Attempts to make model compounds that have chemical and biological activity similar to
the natural compounds have also led to many new synthetic techniques. Two of the many
biological molecules that contain metals are in Figure 1.10. Although these molecules have
very different roles, they share similar ring systems.
One current area that bridges organometallic chemistry and bioinorganic chemistry is
the conversion of nitrogen to ammonia:
N2 + 3 H2 h 2 NH3
This reaction is one of the most important industrial processes, with over 100 million tons
of ammonia produced annually worldwide, primarily for fertilizer. However, in spite of
metal oxide catalysts introduced in the Haber–Bosch process in 1913, and improved since
then, it is also a reaction that requires temperatures between 350 and 550 °C and from
150–350 atm pressure and that still results in a yield of only 15 percent ammonia. Bacteria,
however, manage to fix nitrogen (convert it to ammonia and then to nitrite and nitrate) at
0.8 atm at room temperature in nodules on the roots of legumes. The nitrogenase enzyme
that catalyzes this reaction is a complex iron–molybdenum–sulfur protein. The structure of
its active sites has been determined by X-ray crystallography.5 A vigorous area of modern
inorganic research is to design reactions that could be carried out on an industrial scale
that model the reaction of nitrogenase to generate ammonia under mild conditions. It is
estimated that as much as 1 percent of the world’s total energy consumption is currently
used for the Haber–Bosch process.
Inorganic chemistry also has medical applications. Notable among these is the development
of platinum-containing antitumor agents, the first of which was the cis isomer of Pt(NH3)2Cl2,