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A positive step for silicon chemistry.


Scientists have made a novel form of silicon with potentially new properties to tap. A team of chemists at Northwestern University Northwestern University, mainly at Evanston, Ill.; coeducational; chartered 1851, opened 1855 by Methodists. In 1873 it absorbed Evanston College for Ladies.  in Evanston, Ill. and Indiana University Indiana University, main campus at Bloomington; state supported; coeducational; chartered 1820 as a seminary, opened 1824. It became a college in 1828 and a university in 1838. The medical center (run jointly with Purdue Univ.  in Bloomington has created and identified the first stable silicon cation cation (kăt'ī`ən), atom or group of atoms carrying a positive charge. The charge results because there are more protons than electrons in the cation. , a positively charged ion that has three bonds. Silicon naturally forms two, four, or five bonds.

The new silicon cation may lead to better strategies for synthesizing silicon-based materials, researchers believe.

For the past 50 years, chemists have aspired to make a form of silicon with three bonds. They believed this was possible because carbon, a close relative on the periodic table, can form a "carbocation A carbocation (IPA pronunciation: [kɑ(r)'bəʊkæt'aɪ.ɒn]) is an ion with a positively-charged carbon atom. The charged carbon atom in a carbocation is a "sextet", i.e. ," which also has three bonds and a positive charge. The highly reactive carbocation -- an intermediate in many organic and biological processes - has helped researchers probe the mechanisms behind chemical reactions. Carbocations also serve as industrial catalysts.

But the silicon cation proved more difficult to make than the carbocation. It is more reactive and thus more fleeting. In the June 25 SCIENCE, the researchers describe how they trapped this elusive chemical species.

Led by Joseph B. Lambert of Northwestern University, the group made two key breakthroughs this past year. First, they discovered a good solvent that stabilized the cation. Toluene toluene (tōl`yēn') or methylbenzene (mĕth'əlbĕn`zēn), C7H8  did the trick, although the researchers were surprised that a hydrocarbon solvent readily dissolved this charged molecule.

Second, they identified a negatively charged ion, called an anion anion (ăn`ī'ən), atom or group of atoms carrying a negative charge. The charge results because there are more electrons than protons in the anion. , to pair with the cation. This anion doesn't react with the silicon cation, but prevents it from reacting with other chemicals. It plays a protective role because its negative charge is diffuse, spreading widely over its large molecular structure, which contains 20 fluorine fluorine (fl`ərēn, –rĭn), gaseous chemical element; symbol F; at. no. 9; at. wt. 18.998403; m.p. −219.6°C;; b.p. −188.14°C;; density 1.  atoms, Lambert notes.

Using X-ray crystallography, the researchers obtained an atomic-level picture of their quarry. They determined that it indeed holds the positive charge and is too far removed from the anion, at 4 angstroms, to be considered bonded.

Philip R. Boudjouk, a silicon chemist at North Dakota State University North Dakota State University, at Fargo; land-grant and state supported; coeducational; chartered and opened 1890 as North Dakota Agricultural College, achieved university status in 1960.  in Fargo, calls the work a "very important development in organometallic chemistry." He adds, "The silicon cation is quite a reactive species, so we should be able to do things with it that you normally can't do."

Boudjouk speculates that it may prove useful for catalyzing the formation of polymers. Already, the silicon cation appears to speed the process for making materials used in silicone products, such as lubricants and adhesives, Lambert reports.
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Title Annotation:new silicon cation developed
Publication:Science News
Article Type:Brief Article
Date:Jul 17, 1993
Words:396
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