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Chapter 4 Nomenclature and Conformations of Alkanes and Cycloalkanes

THE CHEMISTRY OF . . .
Elemental Carbon
Carbon as the pure element exists in several forms that are
as different from one another as it is possible to imagine.
Different forms of a pure element are called allotropes. One
allotrope of pure carbon is the very soft and totally black
substance called graphite, the main substance at the center of pencils and the main component of charcoal and chimney soot. Another allotropic form of carbon is diamond, the
colorless brilliant gem that is the hardest of all substances
found in nature. Still another allotrope, perhaps the most
exotic, is called buckminsterfullerene after the inventor of
the geodesic dome, Buckminster Fuller.
The different properties of these allotropic forms arise
from different structural arrangements of the carbon atoms
in each form, and these arrangements result, in part, from
different hybridization states of their carbon atoms. The carbon atoms of diamond are all sp3 hybridized with tetrahedrally oriented bonds. The structure of diamond is what you
would get if you extended the structure of adamantane in
three dimensions. The great hardness of diamond results
from the fact that the entire diamond crystal is one large
moleculea network of interconnecting rings that is held
together by millions of strong covalent bonds.
In graphite the carbon atoms are sp2 hybridized. Because
of the trigonal planar orientation of their covalent bonds, the
carbon atoms of graphite are in sheets. The sheets are actu-

ally huge molecules consisting of fused benzene rings (see

below). While all of the covalent bonds of each sheet lie in
the same plane, the sheets are piled one on another and the
p orbitals of their benzene rings keep them apart. Although
these p orbitals interact, their interactions are very weak,
much weaker than those of covalent bonds, allowing the
individual sheets to slide past one another and accounting
for graphites usefulness as a lubricant.
Buckminsterfullerene (shown on the next page) is a representative of a new class of carbon compounds discovered
in 1985 consisting of carbon clusters called fullerenes (see
Section 14.8C for the story of their discovery and synthesis).
Buckminsterfullerene (also called a buckyball) is a hollow
cluster of 60 carbon atoms, all of which are sp2 hybridized,
and which are joined together in a pattern like the seams of
a soccer ball. The center of the buckyball is large enough to
hold an atom of helium or argon, and such compounds are
known. In the buckyball there are 32 interlocking rings: 20
are hexagons and 12 are pentagons, producing a highly
symmetrical molecule. A smaller symmetrical molecule, synthesized in 1982 by Leo A. Paquette and co-workers at Ohio
State University, is dodecahedrane.
One nal point: We began this book telling of how all of
the carbon atoms of the universe are thought to have been
formed in the interiors of stars and to have been dispersed

A portion of the diamond structure

Carbon is shown here in its diamond

and graphite forms

A portion of the structure of graphite

4.16 Synthesis of Alkanes and Cycloalkanes

throughout the universe when some of those stars exploded
as supernovae. Consider this evidence. Sediments on our
planet, known to be 251 million years old and which were
formed at the time of a great extinction caused by the collision of a comet with Earth, have been found to contain
buckyballs with helium atoms in their centers. The isotopic
ratio of 3He/4He in them is much larger than the ratio in
ordinary helium found on Earth now, indicating that the helium
was of extraterrestrial origin. So in these discoveries we have
fascinating evidence for the origin of elemental carbon and
how some of it got here. Most carbon atoms were produced
when Earth was formed billions of years ago. But the carbon
atoms of the buckyballs found in this sediment, formed
originally in the interior of a star somewhere in the universe,
probably made their way here 251 million years ago in a comet
or meteorite.

Dodecahedrane

177

Buckminsterfullerene

4.15 Chemical Reactions of Alkanes

Alkanes, as a class, are characterized by a general inertness to many chemical reagents.
Carboncarbon and carbonhydrogen bonds are quite strong; they do not break unless
alkanes are heated to very high temperatures. Because carbon and hydrogen atoms have
nearly the same electronegativity, the carbonhydrogen bonds of alkanes are only slightly
polarized. As a consequence, they are generally unaffected by most bases. Molecules of
alkanes have no unshared electrons to offer as sites for attack by acids. This low reactivity
of alkanes toward many reagents accounts for the fact that alkanes were originally called
parafns (parum afnis, Latin: little afnity).
The term parafn, however, was probably not an appropriate one. We all know that
alkanes react vigorously with oxygen when an appropriate mixture is ignited. This combustion occurs, for example, in the cylinders of automobiles, in furnaces, and, more gently, with
parafn candles. When heated, alkanes also react with chlorine and bromine, and they react
explosively with uorine. We shall study these reactions in Chapter 10.

4.16 Synthesis of Alkanes and Cycloalkanes

A chemical synthesis may require, at some point, the conversion of a carboncarbon
double or triple bond to a single bond. Synthesis of the following compound, used as an
ingredient in some perfumes, is an example.
H3CO2C

H3CO2C
(used in some perfumes)

This conversion is easily accomplished by a reaction called hydrogenation. There are several reaction conditions that can be used to carry out hydrogenation, but among the common ways is use of hydrogen gas and a solid metal catalyst such as platinum, palladium,
or nickel. Equations in the following section represent general examples for the hydrogenation of alkenes and alkynes.

4.16A Hydrogenation of Alkenes and Alkynes

Alkenes and alkynes react with hydrogen in the presence of metal catalysts such as nickel,
palladium, and platinum to produce alkanes. The general reaction is one in which the atoms