Catenation

Catenation is the linkage of atoms of the same element

into longer chains. Catenation occurs most readily in
carbon, which forms covalent bonds with other carbon
atoms to form longer chains and structures. This is the
reason for the presence of the vast number of organic
compounds in nature. Carbon is most well known for its
properties of catenation, with organic chemistry essentially being the study of catenated carbon structures (and
known as catenae). However, carbon is by no means the
only element capable of forming such catenae, and several other main group elements are capable of forming an
expansive range of catenae, including silicon, sulfur and
boron.

ample - arising from sigma delocalization of the electrons

in the chain.[3]
Phosphorus chains (with organic substituents) have been
prepared, although these tend to be quite fragile. Small
rings or clusters are more common.
Even siliconsilicon pi bonds are possible. However,
these bonds are less stable than the carbon analogues.
Disilane is quite reactive compared to ethane. Disilylenes
are quite rare, unlike alkenes. Examples of disilynes, long
thought to be too unstable to be isolated[4] were reported
in 2004.[5]
In recent years a variety of double and triple bonds between the semi-metallic elements have been reported, including silicon, germanium, arsenic, bismuth and so on.
The ability of certain main group elements to catenate is
currently the subject of research into inorganic polymers.

The ability of an element to catenate is primarily based on

the bond energy of the element to itself, which decreases
with more diuse orbitals (those with higher azimuthal
quantum number) overlapping to form the bond. Hence,
carbon, with the least diuse valence shell p orbital
is capable of forming longer p-p sigma bonded chains
of atoms than heavier elements which bond via higher
valence shell orbitals. Catenation ability is also inuenced by a range of steric and electronic factors, including the electronegativity of the element in question, the
molecular orbital hybridization and the ability to form
dierent kinds of covalent bonds. For carbon, the sigma
overlap between adjacent atoms is suciently strong that
perfectly stable chains can be formed. With other elements this was once thought to be extremely dicult in
spite of plenty of evidence to the contrary.

1 See also
Concatenation (disambiguation)

2 References
[1] W. W. Portereld, Inorganic Chemistry: A Unied Approach, 2nd Ed., Academic Press (1993), p. 219.
[2] Inorganic Chemistry, Holleman-Wiberg, John Wiley &
Sons (2001) p. 844.

The versatile chemistry of elemental sulfur is largely due

to catenation. In the native state, sulfur exists as S8
molecules. On heating these rings open and link together
giving rise to increasingly long chains, as evidenced by the
progressive increase in viscosity as the chains lengthen.
Selenium and tellurium also show variants of these structural motifs.

[3] Miller, R. D.; Michl, J. (1989).

polymers.
Chemical Reviews.
doi:10.1021/cr00096a006.

Polysilane high
89 (6): 1359.

[4] Karni, M.; Apeloig, Y. (January 2002). The quest

for a stable silyne, RSiCR. The eect of bulky
substituents.
Silicon Chemistry.
1 (1): 5965.
doi:10.1023/A:1016091614005.

Silicon can form sigma bonds to other silicon atoms (and

disilane is the parent of this class of compounds). However, it is dicult to prepare and isolate Si H (analogous to the saturated alkane hydrocarbons) with n greater
than about 8, as their thermal stability decreases with increases in the number of silicon atoms. Silanes higher in
molecular weight than disilane decompose to polymeric
polysilicon hydride and hydrogen.[1][2] But with a suitable pair of organic substituents in place of hydrogen on
each silicon it is possible to prepare polysilanes (sometimes, erroneously called polysilenes) that are analogues
of alkanes. These long chain compounds have surprising
electronic properties - high electrical conductivity, for ex-

[5] Akira Sekiguchi; Rei Kinjo; Masaaki Ichinohe

(September 2004). A Stable Compound Containing a Silicon-Silicon Triple Bond. Science. 305
Bibcode:2004Sci...305.1755S.
(5691): 17551757.
doi:10.1126/science.1102209. PMID 15375262.

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Catenation Source: https://en.wikipedia.org/wiki/Catenation?oldid=722542222 Contributors: Cimon Avaro, Xanthine, Maximus Rex,

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