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Author: Subject: FOX-7 as a ligand
killswitch
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[*] posted on 18-5-2013 at 13:05
FOX-7 as a ligand




I've been looking for something novel to do with energetic materials that also incorporated inorganic chemistry.

1,1-diamino-2,2-dinitroethene has a few unusual characteristics that make it a particularly interesting molecule. It's pretty tiny for an aromatic molecule, quite polar, and has both geminal amines and geminal nitro groups.

Just from looking at this molecule, those amino groups seem to be basic in name only.

I am wondering how it would coordinate to various metals. Would a relatively electropositive element such as manganese, zirconium, or cerium help stabilize the nitro groups and thus coordinate to the left side of the molecule? Could pi-orbital overlap occur without destabilizing the ligand? Would relatively electronegative elements like iron or nickel coordinate to the amines and destabilize the ligand? Can the amines even coordinate at all given how strong the electron withdrawing nitro groups are drawing in the electron density?

And most interestingly of all, could it act as a bridging ligand between relatively electropositive elements like cerium or zirconium and more electronegative ones like nickel or lead?
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Boffis
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[*] posted on 18-5-2013 at 14:23


In Inorganic Chemistry on the ACS web site there are at least two paper concerning describing salts of Fox-7 and metal-amine-Fox-7 complexes where the metal is Cu or Ni. They also describe Ag and K salts and refer to metal aminocomplex salts but it is not clear from the abstracts whether the Fox-7 is acting as a ligand or anion; the later seems more likely.

I'll dig out the references again and post them.
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[*] posted on 19-5-2013 at 10:19


Here's an idea I had a little while ago

www.sciencemadness.org/talk/viewthread.php?tid=9443#pid17013...

I can't say how basic those amines of Fox-7 are but investigation of
co-crystalization with another energetic compound would be warranted.
data sources
www.chemspider.com/Chemical-Structure.467536.html
http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=5367...

.
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Boffis
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[*] posted on 21-5-2013 at 06:42


@ Killswitch the attached excerpt is from a paper by T. T. Vo et al; Inorg Chem.; 2012 and concerns the copper Fox-7 complex; the preparation is also given but is very very simple! Simply mix 1 Mol equi. copper II nitrate and 2 Mol. equi. of fox-7 dissolved in KOH.

In an earlier paper byGarg et al.; Inorg Chem 2011 p390 they describe other reactions of Fox-7 complexes of Ni and Cu with ammonia as a co-ligand. Here they make the point that the hioghly electron withdarwing groups on one end make the fox-7 a weak acid and in the Cu complex appears to be mono basic.

Interesting sounding chemistry! I'd like to play with this stuff. Have you managed to synthesise it?

Attachment: Copper Fox-7 complex Inorg Chem 2012 p1965.pdf (368kB)
This file has been downloaded 278 times

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[*] posted on 25-5-2013 at 10:01


Quote: Originally posted by Boffis  

Interesting sounding chemistry! I'd like to play with this stuff. Have you managed to synthesise it?


Not yet, and it looks like it will be a giant pain in the ass. Having access to acetamidine hydrochloride would easily cut the required work in half. And of course if you have access to 2-methyl imidazole it's practically a 2-step process.

If you don't have acetamidine hydrochloride, you'll need to do this. If you don't have acetonitrile (now that it's been deemed a cancer risk I can't find it in nail polish remover; if anyone has another source I've overlooked please inform us), you'll need to do this:

Quote: Originally posted by BASF  
Detailed Acetonitrile prep instructions. Click the blue link to view the post.
.

Then the diethyl oxalate. Either do a Fischer with oxalic acid and ethanol, or an Sn2 with ethyl chloride and sodium oxalate. If you don't have ethyl chloride, you'll need to look for the instructions in this thread.

If you don't have an alkali alkoxide, you'll need to add elemental lithium from Energizer batteries to absolute methanol.

The synthesis I've seen only requires azeotropic nitric acid, which can be had at hobby shops as a circuit board etchant. I'm unsure whether higher concentrations of nitric acid would improve yield. The nitration mechanism isn't like others I've studied. Is it radical? Or is it a weird-looking but otherwise standard electrophilic aromatic substitution?
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[*] posted on 25-5-2013 at 13:01


Quote: Originally posted by Boffis  


Interesting sounding chemistry! I'd like to play with this stuff. Have you managed to synthesise it?


Yeah, it is a great reaction. Nitrate the 2,6-dihydroxy-4-methylpyrimidine and the tetranitro precipitates out of the acid beautifully. Then quench with water which hydrolyses it and over the next 24h fox7 precipitates as a fluffy yellow fun pile.
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[*] posted on 25-5-2013 at 20:45


Quote: Originally posted by The_Davster  
Quote: Originally posted by Boffis  


Interesting sounding chemistry! I'd like to play with this stuff. Have you managed to synthesise it?


Yeah, it is a great reaction. Nitrate the 2,6-dihydroxy-4-methylpyrimidine and the tetranitro precipitates out of the acid beautifully. Then quench with water which hydrolyses it and over the next 24h fox7 precipitates as a fluffy yellow fun pile.


Which reaction is this? The one I'd intended to use involved nitration of 2-methyl imidazole 4,5-dione.

Is the pyrimidine derivative easier to acquire?
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plante1999
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[*] posted on 25-5-2013 at 21:28


If one want to acquire a kg of the precursor, chinese supplior might do the trick:

http://www.alibaba.com/product-gs/717172013/4_6_Dihydroxy_2_...

Then, you can sell maybe, 30g batch to member here, so it pays for the bulk purchase.

[Edited on 26-5-2013 by plante1999]




I never asked for this.
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[*] posted on 25-5-2013 at 22:25


Quote: Originally posted by plante1999  
If one want to acquire a kg of the precursor, chinese supplior might do the trick:

http://www.alibaba.com/product-gs/717172013/4_6_Dihydroxy_2_...


Does anyone have success with getting chems off alibaba shipped to USA? I have looked on there many times and they had what I wanted but they also sell stuff I wouldn't be caught dead buying.. it makes me think they are not legit or at least somewhat scammy.




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[*] posted on 26-5-2013 at 00:50


Quote: Originally posted by chemcam  
Quote: Originally posted by plante1999  
If one want to acquire a kg of the precursor, chinese supplior might do the trick:

http://www.alibaba.com/product-gs/717172013/4_6_Dihydroxy_2_...


Does anyone have success with getting chems off alibaba shipped to USA? I have looked on there many times and they had what I wanted but they also sell stuff I wouldn't be caught dead buying.. it makes me think they are not legit or at least somewhat scammy.


I have seen one seller that offered 100 METRIC TONS of 99% IPA for 1-2$. SEEMS LEGIT! :D




Rest In Pieces!
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plante1999
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[*] posted on 26-5-2013 at 04:42


Probably 1-2$ per ton/kg. I have done some business with such supplier to get cinnabar, my friend did so, and baugth 3kg of it. As a fine "healing" chemical. Apparently, in china, cinnabar "heal"



I never asked for this.
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[*] posted on 26-5-2013 at 06:19


Quote: Originally posted by killswitch  
Quote: Originally posted by The_Davster  
Quote: Originally posted by Boffis  


Interesting sounding chemistry! I'd like to play with this stuff. Have you managed to synthesise it?


Yeah, it is a great reaction. Nitrate the 2,6-dihydroxy-4-methylpyrimidine and the tetranitro precipitates out of the acid beautifully. Then quench with water which hydrolyses it and over the next 24h fox7 precipitates as a fluffy yellow fun pile.


Which reaction is this? The one I'd intended to use involved nitration of 2-methyl imidazole 4,5-dione.

Is the pyrimidine derivative easier to acquire?


http://pubs.acs.org/doi/abs/10.1021/op068010t?journalCode=op...

I ordered it through a uni lab, so I never sourced it as an individual.

Alibaba is not a scam, but they may have some scammers selling products there. I believe they use an escrow system until delivery. You pay alibaba, company ships you stuff, alibaba releases money to company once received.

[Edited on 26-5-13 by The_Davster]
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[*] posted on 27-5-2013 at 01:56


The amine groups are quite electron-donating to the nitro groups. In fact, the typical diagram of this molecule, which indicates a double carbon-carbon bond, is probably not the most accurate.

Because the amine groups are electron-donating, they actually have a partial positive charge and one would expect them to make poor ligands, if they can act as a ligand at all. My guess is that it can only act as a ligand in anion form.

Just to mention, the whole molecule is very delocalized, "aromatic" would not be an inappropriate term.
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[*] posted on 29-5-2013 at 22:45


Is Fox-7 capable of undergoing diazotization using NaNO2 ?
Like on an aromatic ring .... There is carbon to carbon double bond.




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killswitch
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[*] posted on 11-8-2013 at 09:33


Quote: Originally posted by Motherload  
Is Fox-7 capable of undergoing diazotization using NaNO2 ?
Like on an aromatic ring .... There is carbon to carbon double bond.


The amines are very strongly electron-donating, which makes oxidation very difficult. I would not be overly surprised if the standard NaNO2 + HCl reaction did not work at all.
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[*] posted on 21-8-2013 at 01:07


Quote: Originally posted by killswitch  
The amines are very strongly electron-donating, which makes oxidation very difficult. I would not be overly surprised if the standard NaNO2 + HCl reaction did not work at all.

The typical way to overcome that is to use nitrosylsulfuric acid as the diazotizing reagent, or likewise a simple mix of concentrated sulfuric acid and sodium nitrite (if the acid is too dilute, the nitrosylsulfuric acid will just hydrolyze and release gaseous nitric oxides).

There is of course dinitromethyltetrazole, which consists of the same backbone as the FOX-7. Both hydrogen atoms are on the tetrazole ring, as this tautomer is the most stable. Dinitromethyl tetrazole can form a double anion, this could no doubt act as a ligand to various metal ions. Most likely this would result in cross-linking in the case of bivalent metals such as copper. I am imagining a 1:1 complex of diaminotetrazole with this copper salt of dinitromethyltetrazole.

[Edited on 21-8-2013 by AndersHoveland]
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killswitch
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[*] posted on 25-8-2013 at 06:18


Quote: Originally posted by Adas  
Quote: Originally posted by chemcam  
Quote: Originally posted by plante1999  
If one want to acquire a kg of the precursor, chinese supplior might do the trick:

http://www.alibaba.com/product-gs/717172013/4_6_Dihydroxy_2_...


Does anyone have success with getting chems off alibaba shipped to USA? I have looked on there many times and they had what I wanted but they also sell stuff I wouldn't be caught dead buying.. it makes me think they are not legit or at least somewhat scammy.


I have seen one seller that offered 100 METRIC TONS of 99% IPA for 1-2$. SEEMS LEGIT! :D


Behold the power of currency manipulation!

[Edited on 25-8-2013 by killswitch]
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