madscientist
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N(NN)3N
This compound would liberate approximately 2.55 times as much energy per gram as ethylene glycol dinitrate upon detonation. It would liberate slightly
more moles of gas per gram as ethylene glycol dinitrate. It would be a primary explosive. Here's my proposed route for synthesis:
NCl3 + 3KNH2 ----> N(NH2)3 + 3KCl
N(NH2)3 + 6Cl2 ----> N(NCl2)3 + 6HCl
N(NCl2)3 + N(NH2)3 ----> N(NN)3N + 6HCl
I weep at the sight of flaming acetic anhydride.
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PrimoPyro
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Me Too!
I had a similar idea a few moments ago, actually.
But it just involves:
N(NH2)3 + 3N2O --> N(N3)3
Yours is N8 and mine is N10. Mine is bigger than yours, na na na na. 
PrimoPyro
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madscientist
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NCl3 + 3KN3 ----> N(N3)3 + 3KCl
N2H4 + 4Cl2 ----> N2Cl4 + 4HCl
N2Cl4 + N2H4 ----> N4 + 4HCl
N4 would probably be one of the most stable nitrogen explosives.
On the subject of giant nitrogen molecules, here's a way to build long nitrogen chains that I thought of:
CH3NHCH3 + HNO2 ----> CH3NNOCH3 + H2O
CH3NNOCH3 + NH3 ----> CH3NNNHCH3
CH3NNNHCH3 + HNO2 ----> CH3NNNNOCH3
CH3NNNNOCH3 + NH3 ----> CH3NNNNNHCH3
And so on...
I weep at the sight of flaming acetic anhydride.
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PrimoPyro
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This is fun
Hydrazine would be a great building block.
The only problem is that with each step the danger grows. Also Ive found that sytheses such as these often dont work like you'd expect them to. Trial
and error of sorts....
PrimoPyro
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PrimoPyro
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Hmmm......
If you could just somehow exclude the carbons from this type of reaction by excluding them in the starting substrate, I could see a relatively simple
way of making cyclic all-nitrogen compounds.
All you have to do is prepare one end of the nitrogen chain with an =NH group, as you do with the condensation of NO + NH3. The other end has the NO
group made from NH3+ HNO2.
To bring the ends of the chain together, condense N=O + NH2OH --> N=N-OH
The two ends of the chain are now =N-H and N-OH, dilute the solution greatly (to promote cyclization over straight chain polymerization) and dehydrate
to create the cyclic single bond.
If a six membered chain were cyclized, you'd end up with the nitrogen homolog of benzene. One could reduce this benzene to the all around
-NH-NH-NH-NH-NH-NH- compound, and then nitrate away, or if you are REALLY crazy, build azo chains or something from the H's.
This would be highly dangrous as I would think the ring (hell if you even got THAT far) would self destruct as it became more sensitive to the
reaction conditions the larger you made it, and stuck sensitive N-N single bonds all over the place.
But hey, it'd be neat to try. [laugh]
PrimoPyro
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PHILOU Zrealone
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I really think that if N(NH2)3 existed, we would know it!
Here are the known hydrides of nitrogen:
NH3 (ammonia), H2N-NH2 (hydrazine), HN3 (hydrogen azide), NH4N3 (ammonium azide), H2N-NH3N3 (hydrazinium azide).
So NH3, N2H4, N3H, N4H4 and N5H5 but they are a bit tricky since they are salt combinations of the 3 first!
Other less stable compounds exists: *diazene(diimide) N2H2 (trans HN=NH and isodiazene H2N->N) decomposed at -196 while frozen yellow solid.
*tetrazene (N4H4) trans H2N-N=N-NH2 decomposed above 0°C into N2 and H2N-NH2 (75%) by disproportionation and 25% into NH4N3 by isomerisation.
The first one is made from
H2N-NLi-Ar -->heat decomposition and flash cooling --> HN=NH + Ar-Li.
The second one from
Me3Si-N=N-SiMe3 -SiF4(-50°C)-> (Me3Si)2N-N=N-N(SiMe3)2 -(-78°C CF3CO2H/CH2Cl2)-> H2N-N=N-NH2
So from this you see that poly N sequences are unstable; NH2-NH2 is very stable vs NH2-N=N-NH2...NH2-NH-NH2 and NH2-NH-NH-NH2 aren't even mentionned!
I know some polyaza C containing most of those are 6 membered rings the more the number of N linked to each other the more sensitive the compound so
triazabenzene < tetraazabenzene < pentazabenzene
Also in such molecules -CH=N-N=N-CH- is less stable than -CH=N-CH=N-N-!
The highest lenght chain of N in a C molecule is 5 and it is hell explosive; 8 is only viable at very low temperatures.
NCl3 is hell unstable towards many organics; the reaction you propose would only work in a suitable solvant (NCl3 often goes BOOM in such solvant).
NCl3 + AgN3 would be more like it!
N2H4 won't survive Cl2 attack --> HCl + N2 and heat. N2Cl4 doesn't exist, but N2F4 does...but it is a strong fluorinating agent --> heat and explosion
more than certainly
N2F4 + NH3 (or NH2-NH2) --> N2 + HF + heat
(CH3)2NH + HNO2 -->(CH3)2N-NO
(CH3)2N-NO + NH3 -/-> (CH3)2N-N=NH (not possible)
(CH3)2N-NO + NH2-NH2 --> (CH3)2N-N=N-NH2 (impossible to go further-already quite explosive)
(CH3)2N-NO + H2N-OH --> (CH3)2N-N=N-OH (not further)
N(NH2)3 + 3N2O -/-> N(N3)3 + 3H2O
Unless you think NH2-NH2 + 2N2O --> N3-N3 + 2H2O (what is not the case) and that NH3 + N2O --> HN3 + H2O (what is also not the case).
Na-NH2 + N2O is the only way to go NaN3
And NH2-NH2 + HNO2 is the other way:
NH2-NH3NO2 --> NH2-NH-NO + H2O --> HN3 + N2 + NH3 + H2O (reaction is uncomplete due to decomposition)
N(NH2)3 will not survive Cl2 --> HCl + N2
NH3 + NCl3 --> HCl + N2
Don't expect N chemistry to be the same as C chemistry...way oversimplified vision of the problem!
But some things are stil possible:
R-NH2 + ON-R --> R-N=N-R
So:
(CH3)2N-N=O + H2N-N=N-N(CH3)2 --> (CH3)2N-N=N-N=N-N(CH3) (hell explosive) <-- 2(CH3)2N-N=O + H2N-NH2
You see that you can't make infinite chain of nitrogen, unless you are able to make NH2-(N=N-)n-NO what would imply to oxydise partially and gently
one end!
The recent discovery of NH2-N=N-NH2 allow us to think further:
2(CH3)2N-N=O + NH2-N=N-NH2 --> (CH3)2N-N=N-N=N-N=N-N(CH3)2 but the world record is not yet here (only 8 N chain!) for sure very very unstable (stable
only far below O°C).
PH Z
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PHILOU Zrealone
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Also NH2-N=N-NH2 may give good chances to get a compound of the kind N3NH3-N=N-NH3N3 with HN3 so N10H6 !
(CH3)2N-N=O can react with H2N-R to give (CH3)2N-N=N-R...so maybe it is possible it reacts with NH3 to give (CH3)2N-N=NH althought I haven't seen
mention of this anywhere.
Anyway if it is possible; then
(CH3)2N-N=NH + HO-N=N-N(CH3)2 --> (CH3)2N-N=N-N=N-N(CH3)2 but this is the same as before.
So you see that two limitations occurs:
1)the fact -NO can only be incorporated on a secundary amine R2NH
2)the fact that over 6N chain is suicidal to handle.
PH Z
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Anders Hoveland
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Most of these all nitrogen molecules will decompose to N2. One of the reasons is that they share a resonance state with several N2 groups.
If you can design the molecular arrangement so that not all the N2's can pair up... Some of these might be stable if kept at liquid nitrogen
temperatures, but then the question is how to form it in the first place at such low temperatures. Karl Christe at USC is actually trying to make
tetrazolium tetrazolate N5+ N5-, but the tetrazolate anion has yet to be prepared. They calculate that N5+ will not oxidize N5-, so an ionic salt
allotrope of nitrogen might form. N5+ and azide only react to make N2, even at cold temperatures. There is good reason to expect N5- to exist, it
being quite stable theoretically because of resonance states.
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JohnWW
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According to http://en.wikipedia.org/wiki/Pentazole pentazole, HN5, and the cyclic resonance-stabilized pentazolide anion, N5-, can theoretically exist, and
there is spectrometric evidence for them as intermediate species. Substituted pentazoles, in which the H is replaced by an aromatic organic group,
particularly 4-dimethylaminophenylpentazole, have been isolated and are quite stable up to moderate temperatures. However, the cyclic cation N5+ is
unlikely to be ever isolated or even detected because it is anti-aromatic. See also http://en.wikipedia.org/wiki/Pentazenium , http://en.wikipedia.org/wiki/Tetranitrogen .
Cyclic or linear N compounds with more than 5 Ns in succession, such as hexaazabenzene or hexazine, N6 , see http://en.wikipedia.org/wiki/Hexazine , or polyhedral nitrogen allotropes, or polynitrogen (consisting of infinite chains of N atoms with
alternating single and double bonds like polyacetylene which would result in electrical conductivity), are unlikely to be ever isolated, no matter how
well resonance-stabilized, because of electrostatic repulsion between the unused electron pairs on the N atoms, - except if kept under VERY high
pressure. However, an exception may occur in which, in addition to resonance-stabilization, one of the N atoms is pentavalent, being protonated to
form a tertiary ammonium salt, or being a quaternary ammonium salt. See also:
http://www.qtp.ufl.edu/~bartlett/pdf/polynitrogen.pdf
http://pubs.acs.org/cen/news/8231/8231notw6.html
http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.24....
http://www.intdetsymp.org/detsymp2002/PaperSubmit/FinalManus...
US Patent 5234476
That reminds me: have either of these resonance-stabilized quaternary ammonium cations ever been synthesized:
O=N-N=N(+)=O <===> O=N(+)=N-N=O
O=N-N=N-N=N(+)=O <====> O=N(+)=N-N=N-N=O
[Edited on 20-6-10 by JohnWW]
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gregxy
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If you want the ultimate unobtainable energetic molecule how about :
Li2N-NF2
Adding metals to the structure might be a way to put more energy into a molecule.
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Anders Hoveland
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Karl Christe has in fact already made linear N5+ and found it to be reasonably stable, and he desribes it as being capable of oxidizing bromine. I
wonder what exactly that reaction is.
ONNN+O shares a resonance with ONN and NO+, in other words it will decompose into nitrosyl cation and nitrous oxide.
ONNNNN+O will decompose into N2O, N2, and NO+. Keep guessing.
My opinion: Li2NNF2 should theoretically exist, I do not think it would be very stable at room temperature.
C(NO)(NF2)3 mixed with pentaborane might be an extremely powerful, albight highly sensitive, explosive mixture
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