M-SG reducing agent

Last updated

In M-SG an alkali metal is absorbed into silica gel at elevated temperatures. The resulting black powder material is an effective reducing agent and safe to handle as opposed to the pure metal. The material can also be used as a desiccant and as a hydrogen source. [1]

The metal is either sodium or a sodium - potassium alloy (Na2K). The molten metal is mixed with silica gel under constant agitation at room temperature. This phase 0 material must be handled in an inert atmosphere. Heating phase 0 at 150 °C (302 °F) takes it to phase I. When this material is exposed to dry oxygen the reducing power is not affected. At further heating to 400 °C (752 °F)phase II can be handled safely in an ambient environment.

M-SG reductions: benzyl chloride reduction to bibenzyl, dibenzothiophene reduction to biphenyl and naphthalene reduction to dihydronaphthalene M-SG reducing agent.svg
M-SG reductions: benzyl chloride reduction to bibenzyl, dibenzothiophene reduction to biphenyl and naphthalene reduction to dihydronaphthalene

The metal reacts with the silica gel in an exothermic reaction in which Na4Si4 nanoparticles are formed. The powder reacts with water to form hydrogen.

Compounds such as biphenyl and naphthalene are reduced by the powder and form highly coloured radical anions. The powder can also be introduced in a column chromatography setup and eluted with organic reactants in order to probe the reducing power. The powder is mixed with additional (wet) silica gel which provides additional hydrogen. A Birch reduction of naphthalene takes 5 minutes elution time. The column converts benzyl chloride to bibenzyl in a Wurtz coupling and in a similar fashion dibenzothiophene is reduced to biphenyl.

See also

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

<span class="mw-page-title-main">Sodium carbonate</span> Chemical compound

Sodium carbonate is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water. Historically, it was extracted from the ashes of plants grown in sodium-rich soils, and because the ashes of these sodium-rich plants were noticeably different from ashes of wood, sodium carbonate became known as "soda ash". It is produced in large quantities from sodium chloride and limestone by the Solvay process, as well as by carbonating sodium hydroxide which is made using the chloralkali process.

A substance is pyrophoric if it ignites spontaneously in air at or below 54 °C (129 °F) or within 5 minutes after coming into contact with air. Examples are organolithium compounds and triethylborane. Pyrophoric materials are often water-reactive as well and will ignite when they contact water or humid air. They can be handled safely in atmospheres of argon or nitrogen. Class D fire extinguishers are designated for use in fires involving pyrophoric materials. A related concept is hypergolicity, in which two compounds spontaneously ignite when mixed.

<span class="mw-page-title-main">Silica gel</span> Chemical compound

Silica gel is an amorphous and porous form of silicon dioxide (silica), consisting of an irregular tridimensional framework of alternating silicon and oxygen atoms with nanometer-scale voids and pores. The voids may contain water or some other liquids, or may be filled by gas or vacuum. In the last case, the material is properly called silica xerogel.

Sodium silicate is a generic name for chemical compounds with the formula Na
2x
Si
y
O
2y+x
or (Na
2
O)
x
·(SiO
2
)
y
, such as sodium metasilicate, sodium orthosilicate, and sodium pyrosilicate. The anions are often polymeric. These compounds are generally colorless transparent solids or white powders, and soluble in water in various amounts.

<span class="mw-page-title-main">Molecular sieve</span> Filter material with homogeneously sized pores in the nanometer range

A molecular sieve is a material with pores of uniform size. These pore diameters are similar in size to small molecules, and thus large molecules cannot enter or be adsorbed, while smaller molecules can. As a mixture of molecules migrates through the stationary bed of porous, semi-solid substance referred to as a sieve, the components of the highest molecular weight leave the bed first, followed by successively smaller molecules. Some molecular sieves are used in size-exclusion chromatography, a separation technique that sorts molecules based on their size. Another important use is as a desiccant. Most of molecular sieves are aluminosilicate zeolites with Si/Al molar ratio less than 2, but there are also examples of activated charcoal and silica gel.

<span class="mw-page-title-main">Radical anion</span> Free radical species

In organic chemistry, a radical anion is a free radical species that carries a negative charge. Radical anions are encountered in organic chemistry as reduced derivatives of polycyclic aromatic compounds, e.g. sodium naphthenide. An example of a non-carbon radical anion is the superoxide anion, formed by transfer of one electron to an oxygen molecule. Radical anions are typically indicated by .

<span class="mw-page-title-main">Graphite intercalation compound</span> Class of chemical compounds

In the area of solid state chemistry, graphite intercalation compounds are a family of materials prepared from graphite. In particular, the sheets of carbon that comprise graphite can be pried apart by the insertion (intercalation) of ions. The graphite is viewed as a host and the inserted ions as guests. The materials have the formula (guest)Cn where n ≥ 6. The insertion of the guests increases the distance between the carbon sheets. Common guests are reducing agents such as alkali metals. Strong oxidants also intercalate into graphite. Intercalation involves electron transfer into or out of the carbon sheets. So, in some sense, graphite intercalation compounds are salts. Intercalation is often reversible: the inserted ions can be removed and the sheets of carbon collapse to a graphite-like structure.

<span class="mw-page-title-main">Hexafluorosilicic acid</span> Octahedric silicon compound

Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2
SiF
6
. Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless.

<span class="mw-page-title-main">Sodium formate</span> Chemical compound

Sodium formate, HCOONa, is the sodium salt of formic acid, HCOOH. It usually appears as a white deliquescent powder.

Sodium atoms have 11 electrons, one more than the stable configuration of the noble gas neon. As a result, sodium usually forms ionic compounds involving the Na+ cation. Sodium is a reactive alkali metal and is much more stable in ionic compounds. It can also form intermetallic compounds and organosodium compounds. Sodium compounds are often soluble in water.

A pyrotechnic composition is a substance or mixture of substances designed to produce an effect by heat, light, sound, gas/smoke or a combination of these, as a result of non-detonative self-sustaining exothermic chemical reactions. Pyrotechnic substances do not rely on oxygen from external sources to sustain the reaction.

<span class="mw-page-title-main">Rieke metal</span> Group specially prepared, highly reactive metal powder

A Rieke metal is a highly reactive metal powder generated by reduction of a metal salt with an alkali metal. These materials are named after Reuben D. Rieke, who first described along with an associate in 1972 the recipes for their preparation. In 1974 he told about Rieke-magnesium. A 1989 paper by Rieke lists several metals that are allowed by the periodic table to be produced by his process: Cd, Zn, Ni, Pt, Pd, Fe, In, Tl, Co, Cr, Mo, W, Cu, which in turn are called Rieke-nickel, Rieke-platinum, etc.

A geopolymer is a vague psuedo-chemical term used to describe inorganic, typically bulk ceramic-like material that forms covalently bonded, non-crystalline (amorphous) networks, often intermingled with other phases. Many geopolymers may also be classified as alkali-activated cements or acid-activated binders. They are mainly produced by a chemical reaction between a chemically reactive aluminosilicate powder e.g. metakaolin or other clay-derived powders, natural pozzolan, or suitable glasses, and an aqueous solution that causes this powder to react and re-form into a solid monolith. The most common pathway to produce geopolymers is by the reaction of metakaolin with sodium silicate, which is an alkaline solution, but other processes are also possible.

<span class="mw-page-title-main">Oxygen compounds</span> Different oxidation states of Oxygen

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −12 (superoxides), −13 (ozonides), 0, +12 (dioxygenyl), +1, and +2.

Porous glass is glass that includes pores, usually in the nanometre- or micrometre-range, commonly prepared by one of the following processes: through metastable phase separation in borosilicate glasses (such as in their system SiO2-B2O3-Na2O), followed by liquid extraction of one of the formed phases; through the sol-gel process; or simply by sintering glass powder.

<span class="mw-page-title-main">Ammonium thiocyanate</span> Chemical compound

Ammonium thiocyanate is an inorganic compound with the formula [NH4]+[SCN]. It is an ammonium salt of thiocyanic acid. It consists of ammonium cations [NH4]+ and thiocyanate anions [SCN].

<span class="mw-page-title-main">Lead compounds</span> Type of compound

Compounds of lead exist with lead in two main oxidation states: +2 and +4. The former is more common. Inorganic lead(IV) compounds are typically strong oxidants or exist only in highly acidic solutions.

<span class="mw-page-title-main">Alkoxide</span> Conjugate base of an alcohol

In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as RO, where R is the organyl substituent. Alkoxides are strong bases and, when R is not bulky, good nucleophiles and good ligands. Alkoxides, although generally not stable in protic solvents such as water, occur widely as intermediates in various reactions, including the Williamson ether synthesis. Transition metal alkoxides are widely used for coatings and as catalysts.

References

  1. Alkali Metals Plus Silica Gel: Powerful Reducing Agents and Convenient Hydrogen Sources James L. Dye, Kevin D. Cram, Stephanie A. Urbin, Mikhail Y. Redko, James E. Jackson, and Michael Lefenfeld J. Am. Chem. Soc., 127 (26), 9338 -9339, 2005 doi : 10.1021/ja051786+