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Catenation

Look up catenation or catenate in Wikt ionary, t he free dict ionary.

In chemist ry, catenation is t he bonding of at oms of t he same element int o a series, called a
chain.[1] A chain or a ring shape may be open if it s ends are not bonded t o each ot her (an open-
chain compound), or closed if t hey are bonded in a ring (a cyclic compound). The words to
catenate and catenation reflect t he Lat in root catena, "chain".

Carbon

Cat enat ion occurs most readily wit h carbon, which forms covalent bonds wit h ot her carbon
at oms t o form longer chains and st ruct ures. This is t he reason for t he presence of t he vast
number of organic compounds in nat ure. Carbon is most well known for it s propert ies of
cat enat ion, wit h organic chemist ry essent ially being t he st udy of cat enat ed carbon st ruct ures
(and known as catenae). Carbon chains in biochemist ry combine any of various ot her element s,
such as hydrogen, oxygen, and biomet als, ont o t he backbone of carbon.

However, carbon is by no means t he only element capable of forming such cat enae, and several
ot her main-group element s are capable of forming an expansive range of cat enae, including
hydrogen, boron, silicon, phosphorus, and sulfur.

The abilit y of an element t o cat enat e is primarily based on t he bond energy of t he element t o
it self, which decreases wit h more diffuse orbit als (t hose wit h higher azimut hal quant um number)
overlapping t o form t he bond. Hence, carbon, wit h t he least diffuse valence shell p orbit al is
capable of forming longer p-p sigma bonded chains of at oms t han heavier element s which bond
via higher valence shell orbit als. Cat enat ion abilit y is also influenced by a range of st eric and
elect ronic fact ors, including t he elect ronegat ivit y of t he element in quest ion, t he molecular
orbit al n and t he abilit y t o form different kinds of covalent bonds. For carbon, t he sigma overlap
bet ween adjacent at oms is sufficient ly st rong t hat perfect ly st able chains can be formed. Wit h
ot her element s t his was once t hought t o be ext remely difficult in spit e of plent y of evidence t o
t he cont rary.

Hydrogen

Theories of t he st ruct ure of wat er involve t hree-dimensional net works of t et rahedra and chains
and rings, linked via hydrogen bonding.

A polycat enat ed net work, wit h rings formed from met al-t emplat ed hemispheres linked by
hydrogen bonds, was report ed in 2008.[2]

In organic chemist ry, hydrogen bonding is known t o facilit at e t he format ion of chain st ruct ures.
4-t ricyclanol C10H16O, for example, shows cat enat ed hydrogen bonding bet ween t he hydroxyl
groups, leading t o t he format ion of helical chains;[3] cryst alline isopht halic acid C8H6O4 is built up
from molecules connect ed by hydrogen bonds, forming infinit e chains.[4]

In unusual condit ions, a 1-dimensional series of hydrogen molecules confined wit hin a single wall
carbon nanot ube is expect ed t o become met allic at a relat ively low pressure of 163.5 GPa. This
is about 40% of t he ~400 GPa t hought t o be required t o met allize ordinary hydrogen, a pressure
which is difficult t o access experiment ally.[5]

Silicon

Silicon can form sigma bonds t o ot her silicon at oms (and disilane is t he parent of t his class of
compounds). However, it is difficult t o prepare and isolat e SinH2n+2 (analogous t o t he sat urat ed
alkane hydrocarbons) wit h n great er t han about 8, as t heir t hermal st abilit y decreases wit h
increases in t he number of silicon at oms. Silanes higher in molecular weight t han disilane
decompose t o polymeric polysilicon hydride and hydrogen.[6][7] But wit h a suit able pair of organic
subst it uent s in place of hydrogen on each silicon it is possible t o prepare polysilanes
(somet imes, erroneously called polysilenes) t hat are analogues of alkanes. These long chain
compounds have surprising elect ronic propert ies - high elect rical conduct ivit y, for example -
arising from sigma delocalizat ion of t he elect rons in t he chain.[8]
Even silicon–silicon pi bonds are possible. However, t hese bonds are less st able t han t he carbon
analogues. Disilane is quit e react ive compared t o et hane. Disilene and disilynes are quit e rare,
unlike alkenes and alkynes. Examples of disilynes, long t hought t o be t oo unst able t o be
isolat ed[9] were report ed in 2004.[10]

Phosphorus

Phosphorus chains (wit h organic subst it uent s) have been prepared, alt hough t hese t end t o be
quit e fragile. Small rings or clust ers are more common.

Sulfur

The versat ile chemist ry of element al sulfur is largely due t o cat enat ion. In t he nat ive st at e,
sulfur exist s as S 8 molecules. On heat ing t hese rings open and link t oget her giving rise t o
increasingly long chains, as evidenced by t he progressive increase in viscosit y as t he chains
lengt hen. Selenium and t ellurium also show variant s of t hese st ruct ural mot ifs.

Semimetallic elements

In recent years a variet y of double and t riple bonds bet ween t he semi-met allic element s have
been report ed, including silicon, germanium, arsenic, bismut h and so on. The abilit y of cert ain main
group element s t o cat enat e is current ly t he subject of research int o inorganic polymers.

See also

Backbone chain

Chain-growt h polymerizat ion

Macromolecule

Polyhalogen ions

Polysulfides

References
 1. Oxford English Dictionary, 1st edition (1889) [http://www.oed.com/view/Entry/30197 s.v. 'chain',
definition 4g

2. Salaudeen, A. Abibat; Kilnera, C.A.; Halcrow, M.A. (2008). "A crystalline hydrogen-bonded network with a
poly-catenate topology". Chem. Commun.: 5200–5202. doi:10.1039/B810393C (https://doi.org/10.103
9%2FB810393C) .

3. Morris, D.G. Abibat; Ryder, K.S.; Walker, A.; Muir, K.W; Hix, G.B; Maclean, E.J (2001). "Unusual synthesis
and crystal structure of 4-tricyclanol". Tetrahedron Letters. 47 (2). doi:10.1016/S0040-4039(00)01903-
1 (https://doi.org/10.1016%2FS0040-4039%2800%2901903-1) .

4. Derissen, JL (1974). "The crystal structure of isophthalic acid". Acta Crystallogr. B30: 764–2765.
doi:10.1107/S0567740872004844 (https://doi.org/10.1107%2FS0567740872004844) .

5. Xia, Y. Abibat; Yang, B.; Jin, F.; Ma, Y.; Liu, X.; Zhao, M. (2019). "Hydrogen confined in a single wall
carbon nanotube becomes a metallic and superconductive nanowire under high pressure". Nano Lett.
19 (4): 2537–2542. doi:10.1021/acs.nanolett.9b00258 (https://doi.org/10.1021%2Facs.nanolett.9b0
0258) .

. W. W. Porterfield, Inorganic Chemistry: A Unified Approach, 2nd Ed.", Academic Press (1993), p. 219.

7. Inorganic Chemistry, Holleman-Wiberg, John Wiley & Sons (2001) p. 844.

. Miller, R. D.; Michl, J. (1989). "Polysilane high polymers". Chemical Reviews. 89 (6): 1359.
doi:10.1021/cr00096a006 (https://doi.org/10.1021%2Fcr00096a006) .

9. Karni, M.; Apeloig, Y. (January 2002). "The quest for a stable silyne, RSi≡CR′. The effect of bulky
substituents". Silicon Chemistry. 1 (1): 59–65. doi:10.1023/A:1016091614005 (https://doi.org/10.102
3%2FA%3A1016091614005) . S2CID 97098444 (https://api.semanticscholar.org/CorpusID:9709844
4) .

10. Akira Sekiguchi; Rei Kinjo; Masaaki Ichinohe (September 2004). "A Stable Compound Containing a
Silicon-Silicon Triple Bond". Science. 305 (5691): 1755–1757. doi:10.1126/science.1102209 (https://doi.
org/10.1126%2Fscience.1102209) .

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