Bucky balls and Explosives

If you add three nitro groups to toluene, you get tri-nitro-toluene…TNT.

What if you add nitro groups to Buckminsterfullerine, aka Bucky Balls?

Fullerines are apparently solvent in toluene and benzene, so I assume the creation of nitro explosives hold for fullerine based compounds as well.

Could something like…say, dodeca-nitro-fullerine exist?

(IANAChemist)

Where would you put them?
When you make TNT out of toulene, you replace an H with an NO[sub]2[/sub], but there are no hydrogens in the buckyball!

(Again, I’m not a chemist, so this might be completelly wrong, in which case I’m sure someone will be here shortly to correct me.)

IA(learning to be)AChemist, but I don’t work with buckyballs. Anyway, this sounds right to me. Buckyballs just don’t have any room for anything else as far as I know.

IUsedTBAChemist, and the above is right to an extent. Fullerenes do not have hydrogen atoms attached, however each carbon atom is only attached to three other carbons, so there is a degree of unsaturation there (carbon has a valency of four, i.e. it will form four bonds). In a fullerene, the electrons are delocalised, so you don’t have two single bonds and a double bond on each carbon; you could think of each bond being one and a third bonds.

However, you can make fulleranes, which do have hydrogen atoms attached carbon. There doesnn’t seem to be a lot on the web though, and from what I can recall these are pretty unstable beasts.

Disclaimer: I gave up chemistry some years ago.

The preparation of TNT from toluene involves nitration (by electrophilic substitution) of an aromatic molecule. Fullerene is not aromatic, and cannot be nitrated by the same mechanism as toluene. It is possible to produce nitro compounds by other mechanisms (e.g. in the preparation of nitroglycerin), and it’s even possible to nitrate alkenes. Fullerene would function as an alkene for the purposes of nitration, and it is actually possible to nitrate fullerene (apparently reaction with nitrogen dioxide is one method). A fullerene with six nitro groups is mentioned here.

So, it is possible to make nitrated fullerenes. Whether such a compound would be a practical explosive is a rather different matter. To be an effective explosive, a compound must oxidize rapidly and must produce a large number of gaseous molecules (e.g. nitrogen, carbon dioxide) in its decomposition. TNT is a powerful explosive because its decomposition produces a substantial amount of nitrogen, carbon dioxide and water vapor. A fullerene with six nitro groups would not produce substantially more gas upon oxidation than a fullerene with none. Enthalpy would also need to be considered; fullerene, being a product of combustion itself, cannot be expected to release a very large amount of energy upon decomposition, and I doubt a hexanitrofullerene would release all that much more. A more extensively nitrated fullerene might indeed be a very powerful explosive, but it would also be wildly unstable, probably sufficiently unstable to prevent its manufacture, let alone safe handling. Ring strain and strong repulsive interactions between adjacent nitro groups would probably either make the reaction stop or break the molecule apart well before you made an explosive better than TNT.

What about the plain ol gunpowder design, substituting the fullerines for the carbon or diesel in a mix. Would it provide any benefit?

Mods not bucky balls do not exist (that I am aware of) so we re not discussing explosive manufacture.

There is some work going on with nitrated fullerene and nanotube explosives. However, the Woo Woo faction has gotten ahold of the idea, and the net is chock full of worthless references.
I did manage to find a nice little piece on Nitrogen fullerene explosives. That work looks to be mostly in the theoretical stages.

That researcher looks disturbingly like Bill Gates

Do we really want that much explosive power in the hands of the world’s most successful megalomaniac??

I thought an aromatic compound was any compound in which electrons can move around in a circle of atoms that were linked by alternating single and double bonds. A fullerine is not an aromatic hydrocarbon, like toluene or benzene, of course; it’s more like a sheet of graphite that has been wrapped around into a ball or a tube composed of five and six-carbon rings, the arrangement of which keep it from being flat like graphite, which in its purest form contains only six-carbon rings. Fullerenes are essentially graphenes, aren’t they? And aren’t graphenes aromatic compounds?

A planar arrangement of conjugated (alternating double and single) bonds in a closed ring is not the only requirement for aromaticity. Aromatic systems also must obey Hückel’s rule – they must have 4n+2 pi electrons. A spherical system like a fullerene can also be aromatic if it has 2(N+1)² pi electrons (see here). Some charged fullerenes do have clear aromaticity.

EvilGhandi: Buckyballs, or buckminsterfullerenes (usually called fullerenes) do exist and were discovered in 1985. Still, I don’t think this thread constitutes a discussion on explosive manufacture. The possibility of making explosive fullerenes is still very much theoretical, and it would require extensive knowledge and equipment to produce them. This sort of thing would be done in academic (and perhaps military) labs by people who know what they’re doing, and there is no risk that some unfortunate young or unstable person might hurt themself, except maybe with nitric acid.

Very interesting. Thanks for the link. Should I take from this that C60 has antiaromatic quality? I’m not sure what ambiguous aromaticity means, exactly, which is why I ask. Also, unless I’m mistaken, I thought antiaromatic compounds are reactive as all get go, yet I also thought fullerenes are pretty stable. Anyway, I’m glad to be disabused of my ignorance of the Hukel-Rule requirement, so again, thanks!