10/15/2007

A Mighty Inorganic Kablooie

You couldn't pay me enough money to work with polyazides- that's pretty much the bottom line for me. For some reason, though, these potential molecular bombs have attracted a lot of interest lately. The total synthesis of tetraazidomethane* was finally completed earlier this year, and the synthesis of the complex Ti[N3]4, among other metal-polyazides, was completed a few years back.

Fresh off the heels of their previous successes with metal-azide complexes, those crazy sons of bitches at the Christe group have published the synthesis of more bombs, this time with selenium: the (lame) Se[N3]4, the much more awesome Se[N3]5- and the Chuck Norris special Se[N3]62-. That's right, kids. SIX azide groups on one atom. Six.

Six. That's a lotta firepower in one molecule. (Actually, as it turns out, the pentaazido and hexazido compounds, which are anionic, are more stable than the neutral tetrazido species... but they're still not THAT stable.) Surprisingly, they were able to obtain a crystal structure for the hexaazide- badass. And as one would expect, these nanobombs decompose readily at room temperature via the following pathway:

[Ph4P]2[Se(N3)6] --> 2 [Ph4P]N3 + Se + N2 + A GIANT FUCKING EXPLOSION**

While I'm sure there is always great interest in the inorganic community to study the structure and reactivity of new inorganic complexes, I draw the line at ten feet- where the compound, even in small quantities, has enough force to kill me from ten feet with shrapnel or whatnot. This leads me to propose the following transformation:


This work will (not) be continued and I wish to reserve the field for myself.

*Yes, it's a total synthesis. Suck it.
**Explosion only subtlely reported. Read between the lines. Or just read the "Safety Precautions" section which takes up a sizable chunk of the experimental section.

20 comments:

Liquidcarbon said...

Yeah, let's reserve the field for ourselves. I blogged about tetraazidomethane, too.

For titanium, pentaazidotitanate and hexaazidotitanate were MORE stable than the parent Ti(N3)4. For selenium, it may not be the case, it has another lone pair...

Excimer said...

...and look, just like that, a link magically appeared to your tetraazidomethane post...

ZAL said...

I can't but agree with you about reserving the field of not-working with such things for ourselves. However, if you take a look at Christe's website, you'll find that he published quite a few papers about poliazido metal complexes, and there's even mention of such complex anions as [Nb(N3)7]2- and [Ta(N3)7]2-.
So, it's not six, it's seven. seven.

Ψ*Ψ said...

As incredibly badass as it is to get a crystal structure of an explosive...I would never want to do it. Sounds too much like the stories I've heard about old fluorine chemists...yeah, I'd like to keep both my hands attached to my arms.

milkshake said...

even though metal azides are often very sensitive, they are not the strongest explosives - cyclic nitramine compound pack much bigger punch. (Brisancy depends on released energy + detonation speed + volume of released gases).

There has been funding from military for this work lately - one of the possible application of polyazides is the use as "solid nitrogen" to inflate things like airbags and decoy baloons around nuclear warheads; high shattering power and hight temperature are not required in these applications. Good old NaN3, tetrazoles and hydrazine-bis-azide do reasonably good job.

hegemon359 said...

all right, let's see some sort of fucked up f-block metal with 8 or 10 azides. Then let's hide under the bed and never mention azides again

Anonymous said...

So I'm the only one that finds a compound that wants to explode me strangely alluring?

Excimer said...

actually i think octanitrocubane is more blowuppy than most cyclic nitramines- it has a higher RE than RDX anyway. And I did see that heptaazido compound (seven! SEVEN. wtf?) after I wrote this, but it seems that anionic polyazides are a bit more stable than the neutral ones in general...

Okay, folks. You know what needs to happen now. We need to make... octaazidocubane. Ohhh yes. Go to Chemmunity and make it. You have two weeks. Go.

Ψ*Ψ said...

Y'know, I'd say the Dean Toste special instead of Chuck Norris. Much more badass.

Anonymous said...

From the paper... "All compounds should be handled only on a scale of less than 2 mmol with appropriate safety precautions (safety shields, safety glasses, face shields, leather suits, gloves, and ear plugs)."

Leather suits? WTF?

Anonymous said...

Leather suits, huh? Sounds like Phil Baran chemistry then....

milkshake said...

octanitrocubane was actualy less potent explosive than HNIW (aka CL-20) and was extremely unstable - it could be detonated by contact with pyridine. The problem is denitration because heptanitrocubane already forms very stable anion (similar denitration happens with tetranitromethane to nitroform)
Heptanitrocubane is quite strong explosive but not worth the trouble. The thing is that the detonation speed (and hence brisance) grows disproportionally with density and nitrocubanes do not have dense packing. This whole cubane thing was an academic pursuit that got military funding and lots of spotlight but it is worthless from practical point of view.

Uncle Al said...

1) Do it with Te and get tellurium breath, too. What doesn't kill me makes me suicidal.

2) Link to the bomb site, "Service Temporarily Unavailable

The server is temporarily unable to service your request due to maintenance downtime or capacity problems. Please try again later"

3) Octaazidocubane lacks an oxidizer. Octakis(trifluoromethylperoxy)cubane would be fun. Perhaps add aluminum dust (/_\H_f AlF3).

Ashutosh said...

milkshake, do you have a reference for the use of polyazides in balloons around nuclear warheads?
and why do i suspect that you have read john d. clark's "ignition! an informal history of liquid rocket propellants" which is the most entertaining explosives related book i have ever read.

milkshake said...

I don't have any specific reference apart from the Bulletin of Atomic Scientists and Garwin Archive.

For all I know they can use a tank of pressurized gas for the decoys, or hydrazine with nickel catalyst -previously there was an incentive for reducing weight and size of warhed components ontop of the missile but now that multiple independent reentry vehicles (=up to 10 individual nukes per missile) were banned by treaty I think they have plenty spare capacity for their payload.

(The proposed reliable replacement warhead is actually heavier and more wasteful on plutonium than the W87, W88 design - but with the end of Cold war they have all the plutonium and lift capacity they will ever need)

Ashutosh said...

if they don't have Pu they can always buy some from the terrorists who have cannibalized former Soviet warheads

Liberal Arts Chemist said...

Ah do not knock azides. I got my first research job in a Main Group chemistry lab when a graduate student working on a Tellurium azide cation had 50 mg explode in a metal can and had the explosion neatly shear the ends of his fingers off. While the ends of his fingers were swelled and healing I was hired to "be his hands". Within a month I was working on Tellurium azides but in glass vessels so that when it exploded the container would not focus the blast. Sort of a Main Group version of "The Right Stuff".

Russ said...

Has anyone ever modeled nitrogen triazide? That'd be cool.

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