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DANGER Osmium Tetroxide (OsO4) In Use Oxidizing Agent Severe Irritant Causes Eye Damage Toxic to Liver and

Kidney Authorized Personnel Only

Osmium - Os
Chemical properties of osmium - Health effects of osmium Environmental effects of osmium
Atomic number Atomic mass Electronegativity according to Pauling Density Melting point Boiling point Vanderwaals radius Ionic radius Isotopes Electronic shell Energy of first ionisation Standard potential Discovered by 76 190.2 g.mol -1 2.2 22.5 g.cm-3 at 20C 3045 C 5027 C 0.136 nm 0.067 nm (+4) 13 [ Xe ] 4f14 5d- 6s2 838 kJ.mol -1 + 0.85 V (Os2+/ Os ) Smithson Tennant in 1803

Osmium
Osmium is lustrous, silvery metal, one of the so-called platinum group of metals. It is the densest metal known, althoung only by the narrowest margins. Osmium is uneffected by water and acids, but dissolves with molten

alkalis. Osmium powder reacts slowly with the oxygen of the air and gives off detacteble amounts of osmium tetroxide vapour. Applications The metal is used in a few alloys and in industry as a catalyst. At one time it was to be encountered in the nibs of high-quality fountain pens, compass needles, long-life gramophone needles and clock bearings, thanks to its extreme hardness and corrosion resistance. Osmium in the environment Osmium is mainly found alloyed with other platinum metals, from which it is recovered commercially. The most important ores are either iridosmine and osmiridium. Iridosmine is a rare mineral found in Russia and in North and South America. Less of 100 Kg are produced each year. There is little demand for the metal, which is difficult to fabricate.

Health effects of osmium


Osmium tetroxide, OsO4, is highly toxic. Concentrations in air as low as 10-7 g m-3 can cause lung congestion, skin damage, and severe eye damage. The oxide, in particular, should only ever be handled by a properly qualified chemist. Osmium tetroxide can be absorbed into the body by inhalation of its vapour, by inhalation of its aerosol and by ingestion. Inhalation risk: A harmful contamination of the air can be reached very quickly on evaporation of this substance at 20C. Inhalation: Burning sensation. Cough. Headache. Wheezing. Shortness of breath. Visual disturbances. Symptoms may be delayed. Skin: Redness. Skin burns. Pain. Skin discoloration. Blisters. Eyes: Redness. Pain. Blurred vision. Loss of vision. Severe deep burns. Ingestion: Abdominal cramps. Burning sensation. Shock or collapse. Chemical dangers: The substance decomposes on heating producing fumes of osmium. The substance is a strong oxidant and reacts with combustible and reducing materials. Reacts with hydrochloric acid to form toxic chlorine gas. Forms unstable compounds with alkalis. Effects of short-term exposure: Tear drawing. The substance is corrosive to the eyes, the skin, and the respiratory tract. Inhalation of this substance may cause lung oedema. Exposure to high concentrations may result in death. The effects may be delayed. Effects of long-term or repeated exposure: Repeated or prolonged contact with skin may cause dermatitis. The substance may have effects on the kidneys.

Environmental effects of osmium

No information found in our select references. However we expect osmium ecotoxicity to be very low because of its strength as an oxidizer, that makes it be readily converted to the dioxide, a form of the metal that is reasonably innocuous.

Dihydroxylation: a. Example

b. Mechanism

Dihydroxylation occurs via the reaction of an alkene with osmium tetroxide. A cyclic osmate intermediate is formed which is cleaved in a second separate step with sodium bisulfite. Note: You are not responsible for this mechanism. However, be aware that the two hydroxyl groups are added to the same side of the alkene resulting in syn stereochemistry. Oxidative cleavage of 1,2-diols: a. Example

b. Mechanism

You are not responsible for this mechanism. However, realize that a 1,2-diols are oxidatively cleaved to form a dicarbonyl compound. Note: If the 1,2-diol is part of an open chain molecule, then two carbonyl compounds are produced. If the diol is part of a ring system (as in this example, then a single dicarbonyl compound is produced.

Osmium tetroxide (OsO4)


Dr Mike Thompson
Winchester College, UK

Osmium tetroxide (right) is probably the best-known compound of Osmium, which can easily be found, as it is just two places below Iron in the Periodic Table. Osmium tetroxide is inextricably linked to the discovery and subsequent purification of Osmium.
Osmium Osmium is a scarce metal found in only 0.005 ppm of the Earth's crust. Tennant discovered Osmium in 1803 in the residues left behind when crude Platinum and other precious metals had been dissolved in aqua regia (c.HNO3/c.HCl). It is named from the Greek word for odour (osme). Osmium is also found, often with Ru and Ir, in the anode sludges produced during the electrolysis of Nickel (II) solutions. Osmium has an exceptional density of 22.57 g cm-3 and a very high m.p. of 3045C.

Flow diagram showing the extraction of osmium via OsO4


Osmium tetroxide

Osmium tetroxide, also known as osmium(VIII)oxide, formula OsO4, is an example of the highest oxidation achieved by a transition element. Like methane (CH4), osmium tetroxide has a tetrahedral geometry with the OOs-O bond angle(s) approximating 109.5. It is an extremely toxic crystalline solid with a low m.p = 40C and bp = 130C. The powerful combination of high toxicity and high volatility (easily evaporates) makes osmium tetroxide dangerous if not stored or handled correctly. Recent media exposure suggested its use as a 'billionaires' chemical weapon. This Molecule of the Month article is written to show how important this reagent is, to the chemical community, and how it was party to the awarding the Nobel Prize in Chemistry in 2001 to K. Barry Sharpless.

Osmium tetroxide is probably colourless (Butler and Harrod, Inorganic Chemistry: Principles and Applications, p.343) but is sometimes described as yellow (see photo above). I suggest this discrepancy lies with the presence of the impurity OsO2, which is yellow-brown in colour (Cotton and Wilkinson, Advanced Inorganic Chemistry, p.1002). It is very soluble in CCl4 (carbon tetrachloride = tetrachloromethane) and moderately soluble in water. OsO4 has a characteristic ozone-like odour. The smell is recognisable

as the 'fresh' smell you get by old photocopiers, near someone welding, or to be sniffed at on a sunny summers day in a heavily congested city. Should you be close to a lightning strike you will smell ozone, and this is far more likely than being close to a terrorist atrocity. Osmium tetroxide is particularly hazardous to the eyes as it is readily reduced by living tissue to give a black oxide and or the metal. For this reason it finds itself an important use as a Biological Stain when in dilute aqueous solutions.
Specialized use in Organic Chemistry

OsO4 is a convenient reagent for the same side (syn) addition of two OH groups across a carbon-carbon double bond. Osmium tetroxide was first given this use back in 1936 by Criegee and a good source of information on this powerful oxidizing agent is to be found in Schroder, Chem. Rev. 80, 187-213 (1980).

This is a rather slow addition but has the distinct advantage of being almost quantitative, an important consideration when performing multi-step syntheses of natural products. A more familiar reagent that also adds two OH groups across a double bond is alkaline KMnO4. This is a reaction, which used to be taught at A-level and perhaps more interesting than the often-quoted 'decolourises bromine water' test for unsaturation.

The high cost of osmium tetroxide does not preclude its use by perennially under funded chemical research groups. Fortunately, the same reaction can be achieved catalytically. Either H2O2 with OsO4 (Milas & Sussman, J. Am. Chem. Soc., 58, 1302 (1936) or Nmethylmorpholine-N-oxide with OsO4 (VanRheenan, Kelly and Cha, Tet. Lett, 1973 (1976). I also made use of this reagent during my own research with Professor Pettit, J. Chem. Soc. Chem. Commun. 1994, 2725-6.
Preparation of Osmium Tetroxide

Addition of oxygen (oxidation) is possible by burning the metal at 800C. Os + 2 O2 OsO4

An alternative preparation is the oxidation of osmium salts with c.HNO3. This is a widely used method to recover osmium via the volatile osmium tetroxide.
Reactions

OsO4 is a more powerful oxidizing agent than the halogens. It oxidizes the halides (Cl(aq), Br-(aq), I-(aq)) to their respective halogens. One easy way to recognise oxidations is an increase in oxidation number (from 1- of the halides to 0 for the elemental halogens). 2 Cl- (aq) OsO4 + 2 OH- (aq) Cl2

[OsO4(OH)2]2- [deep red]

The above reaction is interesting for a number of reasons, i.e. surprising colour change, osmium expands its coordination sphere to six, the product is diamagnetic and the OH groups are trans (opposite each other).
Conclusion

Osmium tetroxide is a valuable tool in the research of both biologists and chemists, and needs to remain so. Chemists need to protect their interests, perhaps more overtly in future, and ensure that they continue with their important work against the tide of negative publicity concerning the misuse of chemicals by non-chemists.

Net addition occurs because none of the substituents are a leaving group

we could have used NaBH4 as a proton source but its concentration is low compared to the solvent, so we use CH3OH instead Although NaBH4 is a good source of creating a new CH bond, it does not react with anything that is less reactive than an aldehyde or a ketone The reduction of an aldehyde You get exactly the same organic product whether you use lithium tetrahydridoaluminate or sodium tetrahydridoborate. For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to UK A level examiners. [H] means "hydrogen from a reducing agent". In general terms, reduction of an aldehyde leads to a primary alcohol.
Note: If you aren't sure about types of alcohol it is essential to follow this link before you go on. You only need to read the beginning of that page. Use the BACK button on your browser to return to this page.

The reduction of a ketone Again the product is the same whichever of the two reducing agents you use. For example, with propanone you get propan-2-ol:

Reduction of a ketone leads to a secondary alcohol.

Reaction details
Using lithium tetrahydridoaluminate (lithium aluminium hydride) Lithium tetrahydridoaluminate is much more reactive than sodium tetrahydridoborate. It reacts violently with water and alcohols, and so any reaction must exclude these common solvents. The reactions are usually carried out in solution in a carefully dried ether such as ethoxyethane (diethyl ether). The reaction happens at room temperature, and takes place in two separate stages. In the first stage, a salt is formed containing a complex aluminium ion. The following equations show what happens if you start with a general aldehyde or ketone. R and R' can be any combination of hydrogen or alkyl groups.

The product is then treated with a dilute acid (such as dilute sulphuric acid or dilute hydrochloric acid) to release the alcohol from the complex ion.

The alcohol formed can be recovered from the mixture by fractional distillation.

Note: You can see why UK A level examiners are happy with the equations showing H in square brackets! On the other hand, you may well be expected to know that the reaction is done initially in solution in ethoxyethane followed by treatment with acid. The practical details above are simplified to what you are likely to need in a theory exam. In practice, there is an additional step for safety reasons. In particular, if you added dilute acid to the reaction without first removing any excess of LiAlH4, there is an explosion risk because of the violent reaction between the excess LiAlH4 and water in the dilute acid. Some un-dried ethoxyethane is added first before you add the acid. (Remember that the initial reaction is carried out in carefully dried ethoxyethane.) Traces of water in this react with the excess LiAlH 4. Because there are only traces present, the reaction is controllable.

Using sodium tetrahydridoborate (sodium borohydride) Sodium tetrahydridoborate is a more gentle (and therefore safer) reagent than lithium tetrahydridoaluminate. It can be used in solution in alcohols or even solution in water provided the solution is alkaline. I have a problem over describing the reaction conditions, because it seems to be used in so many different ways. Practical details found from various university sites vary widely, and don't necessarily agree with what theoretical sources say! In what follows, I am choosing one out of many different methods. I have chosen this one largely because I think I understand what is going on! Solid sodium tetrahydridoborate is added to a solution of the aldehyde or ketone in an alcohol such as methanol, ethanol or propan-2-ol. Depending on which recipe you read, it is either heated under reflux or left for some time around room temperature. This almost certainly varies depending on the nature of the aldehyde or ketone. At the end of this time, a complex similar to the previous one is formed.

In the second stage of the reaction, water is added and the mixture is boiled to release the alcohol from the complex.

Again, the alcohol formed can be recovered from the mixture by fractional distillation.
New

What about reduction? Similarly, there are specific reagents for the reduction of aldehydes and ketones to alcohols. (See Brown, Sec. 11.10B). Two important ones are sodium borohydride (NaBH4) and lithium aluminum hydride (LiAlH4). Their use is illustrated in the following two examples.

Since there is no carbon-carbon bond breaking which occurs in these reactions, we might expect that these reagents would also reduce ketones to alcohols. That is indeed the case, as seen in these examples.

If we compare the outcome of reduction of aldehydes to that of reduction of ketones, we notice that aldehydes produce primary alcohols while ketones produce secondary alcohols. This give us an alternate method to the Grignard addition for making these types of compounds. (Now would be a good time to make a personal list of reactions which produce alcohols, together with the necessary reagents and the specific structural types involved.)

The comparison of these reduction reactions with the Grignard addition suggests another important point. In these reductions, hydrogen atoms are added to the carbonyl carbon and to the carbonyl oxygen. Since there is no hint of acid present, these reactions resemble base-catalyzed

addition of water, addition of HCN, and the addition of a Grignard reagent rather than acid catalyzed reactions. We may expect them to begin with the attack of a nucleophile at the carbonyl carbon. In order to arrive at the observed product, the effective nucleophile has to be :H-, just as in the addition of a Grignard reagent, the nucleophile was effectively :R-. We justified that statement for the Grignard reagent by examining the carbon-magnesium bond and arguing that it was very strongly polarized so that the carbon effectively controlled the bonding pair of electrons, making it behave like :C-. Can we do something similar for the hydrogen in sodium borohydride or lithium aluminum hydride? First, we need to realize that sodium borohydride is a salt which is made up of a sodium cation (Na+) and a borohydride anion (BH4-) The sodium ion plays no important role in the reaction, so we will ignore it (ions like sodium and potassium are seldom directly involved in reactions. They are present merely to maintain charge balance so that stable compounds can be added to reaction mixtures. They are often called spectator ions.) The borohydride ion is the important player in this process, and it is the B-H bond that we want to examine. A quick glance at the periodic table to review electronegativities tells us that both boron and aluminum are metals with relatively low electronegativities. Each is less electronegative than carbon, and since hydrogen has about the same electronegativity as carbon we can conclude that the B-H bond is polarized with the boron positive and the hydrogen negative. This is very similar to the way we understood the electronic situation in a Grignard reagent, so we conclude that the B-H bond effectively serves as a source of hydride ion (:H-). This is summarized below.

With this information and the addition of a Grignard reagent as a pattern, we can arrive at the following mechanism for the reduction of an aldehyde by sodium borohydride.

Notice the familiar pattern: Attack by a nucleophile at the carbonyl carbon, followed by protonation of the carbonyl oxygen. The same mechanism applies to the reduction of ketones by sodium borohydride and to reactions of carbonyl groups with lithium aluminum hydride. In the latter case, lithium aluminum hydride

is itself highly reactive with water, so the water is added after the lithium aluminum hydride has reacted.

We have one major topic in carbonyl chemistry to introduce -- the reactions which occur at the carbon attached to the carbonyl carbon. This carbon is called the alpha-carbon. Here's an example of such a reaction.

We can pick out several important features of this reaction from this example. First, there are two alpha carbons, but only one undergoes a reaction. That one (on the left) is attached to a hydrogen in the reactant. Second, we notice that there is no reaction at the beta-C-H bonds. Reactivity is restricted to the C-H bond on a carbon directly to the carbonyl carbon. This type of reaction requires an alpha-C-H bond. In a sense, the presence of the carbonyl group next to this C-H bond makes it a functional group. Now to consider a mechanism. Our mechanism must account for the formation of a carbonbromine bond and an oxygen-hydrogen bond (in water) and the cleavage of a carbon-hydrogen bond (alpha) and a bromine-bromine bond. It must also suggest a role for the OH-. so let's begin by speculating that the hydroxide ion acting as a base makes a bond to the alpha-hydrogen. This process is coupled to the breaking of the alpha-C-H bond, whose electrons are then transferred to the alpha-carbon.

This is striking, because we are proposing that the alpha-hydrogen is acidic enough to be removed by a base no stronger than OH-. This is certainly not true of other C-H bonds, and it is only true here to the extent that the equilibrium constant for this step is very small. There is very little of the product of this step at equilibrium (we'll call this product an enolate, for reasons which will make more sense a bit later). What is it about an enolate ion which allows it to be made at all. Put another way, why is the enolate ion stable enough to be formed, while a similar ion made from another C-H bond isn't. When we're looking for reasons of stability, resonance is one of the ideas we should explore. Since this process requires the carbonyl group next door, that resonance should involve the carbonyl group.

Sure enough, if we move electrons as indicated by the curved arrows, we find an alternative resonance structure. This structure has the energetic advantage that the unshared electron pair is on the oxygen (the more electronegative atom) rather than the carbon. And, the resonance itself contributes to lowering the energy of the enolate, which makes it stable enough for a little of it to be formed at equilibrium. It is important to re-emphasize that none of this can happen if the carbonyl group is not next door to reactive C-H bond. The alpha carbon in the enolate is all set up to behave as a nucleophile, providing a pair of electrons to make a new bond to a molecule of bromine. This requires that the bromine-bromine bond be broken at the same time. Notice that either resonance structure can be used to deliver the needed pair of electrons to make the carbon-bromine bond. This is necessarily so, since the two resonance structures are alternate descriptions of the same resonance hybrid.

Bromine is behaving as an electrophile, not because it has a vacancy in a valence orbital, but because it can simulate such a vacancy by breaking a bond. This reminds us of the behavior of the pi bond in a carbonyl group when it reacts with a nucleophile at the carbon atom.

There are some questions that are routinely asked, so let's take them up here. 1. Why does the OH- attack the alpha C-H bond rather than the carbonyl carbon?

It attacks both, but the attack at the carbonyl carbon leads to the hydrate - the product of addition of water. This certainly occurs, but it leads nowhere since the hydrate is present in very small quantities at equilibrium for ketones and most aldehydes. 2. Why does the reaction with molecular bromine take place at the carbon only? After all, there is a potentially nucleophilic unshared electron pair on oxygen as well.

Reaction can take place at the oxygen, but the compound formed with a covalent bond between two rather electronegative elements is less stable than the one which results from reaction at the alpha-carbon.