成鏈:修订间差异

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2011年5月4日 (三) 13:36的版本

成鏈 是指一個化學元素經由連續的共價鍵互相連接形成長鏈狀的分子。碳是最容易以此性質互相連接形成長鏈元素的結構,所以自然界才會有如此多的有機物質,而有機化學實質上就是在研究碳利用這個性質所形成的化合物。不過,碳並不是唯一一個擁有此性質的元素,其他的元素向矽和硫也有此性質。

The ability of an element to catenate is primarily based on the bond energy of the element to itself. This ability is also influenced 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 different kinds of covalent bonds. For carbon, the sigma overlap between adjacent atoms is sufficiently strong that perfectly stable chains can be formed. With other elements this was once thought to be extremely difficult in spite of plenty of evidence to the contrary.

The remarkable properties of elemental sulfur are 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.

Silicon can form sigma bonds to other silicon atoms (disilane is the parent of this class of compounds). But with a suitable pair of organic substituents in place of hydrogen on each silicon it is possible to prepare polysilylenes (sometimes, erroneously called polysilanes) that are analogues of alkanes. These long chain compounds have surprising electronic properties - high electrical conductivity, for example - arising from sigma delocalization of the electrons in the chain. (Ref. R.D. Miller and J. Michl. Chem Rev 89 (1989), pp. 1359–1410.)

Phosphorus chains (with organic substituents) have been prepared, although these tend to be quite fragile. Small rings or clusters are more common.

Even silicon–silicon 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 [1] were reported in 2004.[2]

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.


參考文獻

  1. ^ Karni, M.; Apeloig, Y. The quest for a stable silyne, RSi≡CR′. The effect of bulky substituents. Silicon Chemistry. 2002, 1 (1): 59–65. doi:10.1023/A:1016091614005.  已忽略未知参数|month=(建议使用|date=) (帮助)
  2. ^ Akira Sekiguchi, Rei Kinjo, Masaaki Ichinohe. A Stable Compound Containing a Silicon-Silicon Triple Bond. Science. 2004, 305 (5691): 1755–1757. PMID 15375262. doi:10.1126/science.1102209.  已忽略未知参数|month=(建议使用|date=) (帮助)[1]