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Author: Subject: Exotic Primaries - Complex Salts
Rosco Bodine
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[*] posted on 20-2-2013 at 20:23


Here are a couple of additional articles of interest.

Attachment: nhn1.pdf (175kB)
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Attachment: JSIR 63(8) 677-681.pdf (70kB)
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[Edited on 21-2-2013 by Rosco Bodine]
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[*] posted on 20-2-2013 at 22:47


Metal Hydrazine Complexes , Patents
US 5970703 , US 6481746
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[*] posted on 25-2-2013 at 03:49


Apparently co-crystallized compounds of Cyanides with Nitrites have been noted
but out of sight and earshot of the mainstream , as mentioned halfway down here _
www.guidechem.com/reference/dic-15333.html ( See " Reactivities and Incompatibilities " )
( Just as I said in my post above here )
" Mixtures of Sodium Nitrite and various Cyanides explode on heating, including Potassium Cyanide,
Potassium Hexacyanoferrate(III), Sodium Pentacyanonitrosylferrate(II), Potassium Hexacyanoferrate(II),
or Mercury(II) Cyanide. Such mixtures have been proposed as explosives, initiable by heat or a detonator.
A mixture of Sodium Nitrite and Potassium Thiocyanate explodes on heating.
There is no interaction between Sodium Nitrite and Sodium Thiosulfate in solution, but evaporation
of the mixture gave a residue which explodes on heating. The mixed solids behave similarly."

__________________________________________


- and now for something completely different

Na2NO2 , Disodium Nitrite ? Huh
http://sodium.atomistry.com/disodium_nitrite.html

See bottom of page " 10 Miscellaneous Cathodic Reductions "
http://books.google.com/books?id=6ghTyzzOzM8C&lpg=PA74&a...

An excerpt from " Reduction of Inorganic Substances "
http://tera-3.ul.cs.cmu.edu/NASD/4dcb85c3-9fee-4c83-9e6d-fe6ce5522b59/China/disk1/46/31004737/PDF/00000119.pdf

Disodium Nitrite, an Additive Compound of Sodium Nitrite and Sodium
http://pubs.rsc.org/en/content/articlelanding/1917/CT/ct9171...

Electroreduction of Nitrate to Nitrite to Hydronitrite
http://jes.ecsdl.org/content/101/5/229.abstract

Mellor 8: Supp. 1, 546 (1964) obtained this from NH4NO3 with sodium

.
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Rosco Bodine
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[*] posted on 16-3-2013 at 23:06
trimethylammoniumpentazidodicuprate


A similar complex to Diazidodiamminocopper(II) described on page 8 of this thread is a related Trimethylamine complex or compound salt trimethylammoniumpentazidodicuprate

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

Quote: Originally posted by Taoiseach  
was prepared according to

CuSO4*5H2O + 2NH3 + 2NaN3 ---> [(NH3)2(N3)2Cu] + Na2SO4 + 5H2O

NH3 was added to a solution of CuSO4 until the precipate of Cu(OH)2 redissolved. A saturated warm solution of NaN3 was added. Upon cooling and addition of an equal volume of ethanol, a nice crop of [(NH3)2(N3)2Cu] precipated.

Green-blue glistering crystals. Unlike copper azide these are not friction sensitive. Explodes upon flame contact.

Obviously the compound is oxygene-deficient, so addition of a strong oxidizer should increase its power.



trimethylammoniumpentazidodicuprate is a similar compound about which I can find very little information. It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide. It would seem possible that different metals may also form analogous compounds as does copper.

See attached excerpt from PATR for description of

trimethylammoniumpentazidodicuprate

(CH3)3N-HN3-2[Cu(N3)2]


Attachment: TMA - PATR Vol. 9 Q-T.pdf (103kB)
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[Edited on 17-3-2013 by Rosco Bodine]
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[*] posted on 17-3-2013 at 10:23


Quote: Originally posted by Rosco Bodine  
It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide.

(CH3)3N-N3-2[Cu(N3)2]

dark red crystals, explodes at 201°


I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.

I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably also be too electron-withdrawing.

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(CH3)3N]3Ni+1(N3)3 • (ClO4)

The nickel center can only complex to 6 ligands, so that would leave a +1 ionic charge, so that perchlorate could be part of the complex salt also.

The electronic configuration of the nickel in this proposed compound would correspond to the nickel complex NiF62−, which has been described in the literature.

It could perhaps be prepared by reacting nickel(II) perchlorate with trimethylamine in excess hydrazoic acid.

[Edited on 17-3-2013 by AndersHoveland]
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Rosco Bodine
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[*] posted on 17-3-2013 at 11:28


Quote: Originally posted by AndersHoveland  
Quote: Originally posted by Rosco Bodine  
It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide.

(CH3)NH-N3-2[Cu(N3)2]

I think perhaps you mean (CH3)3N-N3-2[Cu(N3)2]


You are correct ....my typo above has been edited to show "3" for the trimethyl and I see it would also be better to show the trimethylamine as hydro-azide analogous to TMA hydrochloride...which is what I think is probably the case here. If I am on the right track then an anlogous compound may be possible with chlorides as is showing for the azides.

Quote:

I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.

I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably also be too electron-withdrawing.

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(CH3)3N]2Ni+2(N3)4 2(ClO4-)

The nickel center can only complex to 6 ligands, so that would leave a +2 ionic charge, so that perchlorate could be part of the complex salt also.

[Edited on 17-3-2013 by AndersHoveland]


I'll have to do some reading on these complexes to be sure.
My first inclination would be to disagree about the metal being "complexed" by the azide, as it would be more my inclination to expect the complexation involves the substituted ammonia with the metal to form the complex which then forms a mixed salt or compound salt with the uncomplexed metal salt. The complexation of the metal by the substituted ammonia would seem to be analogous for what happens with complexation by hydrazine or semicarbazide, where an "ammonia value" is present as some multiplier. However that value is 0 for trimethylamine, which does not form a complex with copper. It seems almost as if part of the compound is trimethylamine "hydro"-azide which exists or can exist as a distinct compound, cocrystallized as a double salt with 2 copper azides.

This behavior may be peculiar because trimethylamine does not form a complex with copper as does ammonia.
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[*] posted on 17-3-2013 at 11:36


The article listed the possible formulas as either:
Quote:

(CH3)2NH[(N3)2CuN3Cu(N3)2 or

(CH3)3N.HN3.2[Cu(N3)2]


It seems they were not entirely sure what the structure actually was. I think the name "trimethylammoniumpentazidodicuprate" is therefore probably very misleading.

Perhaps I am just overthinking this too much, and the salt just consists of trimethylammonium cations and Cu(N3)3 complex anions.

[Edited on 17-3-2013 by AndersHoveland]
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Rosco Bodine
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[*] posted on 17-3-2013 at 11:45


Yeah it is intriguing huh. It sort of looks like a complex ...but not exactly, and may simply be a multiple salt.....which is what my impression was that led me to speculate even other multiple salts could form as series. But it may not follow at all that way because it could just be a peculiar anomaly that is true for only this one case. Clearly some other investigators were definitely scratching their heads looking at this one ......and we can agree it is red. :D

And it is energetic ...but what are its properties?

Anyway it's a possible "green energetic" so it caught my notice.

Just for giggles Google

trimethylammoniumpentazidodicuprate

What do you get ? :D

Consider the possibility that a compound salt could form between Trimethylamine Perchlorate and Copper Azide , now that would be interesting.

All right Klapotke, enough loafing, time to get back to work :D

[Edited on 17-3-2013 by Rosco Bodine]
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[*] posted on 21-3-2013 at 15:38
metal carbohydrazide complexes


With regards to my post on the preceding page

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

there is information in the hydrazine thread which has bearing upon preparation of carbohydrazide from hydrazine cyanurate but this is uninvestigated and will require experimental confirmation.

http://www.sciencemadness.org/talk/viewthread.php?tid=1128&a...

Also one of the articles which was posted previously as an attachment evidently has too long of a name and is not downloading true as a pdf so I am attaching the name edited file here.

Attachment: Talawar Studies on Lead free initiators metal complexes of carbohydrazide.pdf (415kB)
This file has been downloaded 2222 times

In my earlier post is a typo which I need to correct or clarify
Where I wrote "semicarbazide" should be corrected to read "carbohydrazide" as is the context for the attached article.....even though the same may be true for the semicarbazide complex analogue, I have not yet found references for the semicarbazide complex to verify this.

"With regards to the semicarbazide [should read carbohydrazide] complex of nickel perchlorate or in the alternative the more expensive cobalt perchlorate, these compounds appear to be very promising as fairly easily made initiators."

Attached is an article of interest Thanks to gsd

Chemistry of carbohydrazide and thiocarbohydrazide
Frederick. Kurzer, Michael. Wilkinson
pp 111–149
Publication Date: February 1, 1970 (Article)

franklyn mentions that carbohydrazide is also known as diaminourea ( DAU )
http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...




Attachment: THE CHEMISTRY OF CARBOHYDRAZIDE AND THIOCARBOHYDRAZIDE.pdf (850kB)
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Attachment: Explosives Based on Diaminourea (carbohydrazide).pdf (240kB)
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[Edited on 22-3-2013 by Rosco Bodine]
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[*] posted on 10-6-2013 at 22:25


I just had an idea, I thought I would mention it here.

Take a look at the structure of Manganese(III) acetate. It has a surprisingly complicated inter-coordination structure. Each cluster consists of 3 manganese atoms, 6 acetate groups, a central oxygen atom, and each cluster has a positive charge, typically with an extra outside acetate ion associated with it. The bonding in the cluster is very delocalized, I would draw an analogy to acetylacetone with copper ions (copper acetylacetonate is almost aromatic).

So would it be possible to use dinitrosomethanate in place of the acetate? (dinitrosomethane has an aci-tautomer)
That would leave a positively charged cluster, and then presumably some other oxidizing anion like perchlorate or nitroformate could be associated with it.

Mn3O[CH(NO)2]3+ C(NO2)3

The cluster also has 3 water molecules of hydration, not shown, but those could possibly be replaced with NH3.

resonance diagram of dinitrosomethanate ion:
O=N‒CH=N‒O <--> O‒N=CH‒N=O

resonance diagram of formate ion:
O=CH‒O <--> OCH=O
similar to acetate ion

[Edited on 11-6-2013 by AndersHoveland]
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[*] posted on 19-8-2013 at 13:01


While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?
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[*] posted on 27-8-2013 at 01:26


Quote: Originally posted by papaya  
While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?


The facts are that...
Zn nitrate forms a stable hydrazine complex
Ni (II) nitrate forms a stable hydrazine complex
Cd(II) nitrate forms a stable hydrazine complex
Co (II) nitrate forms a stable hydrazine complex
But...
Cu (II) nitrate forms an unstable hydrazine complex
Hydrazine and iodine or iodate are uncompatible...
Silver nitrate is unstable towards hydrazine...

So watching closely to the oxydoredox potential table
There must be an electrochemical explanation to this...
See hydrazine at potential at +0,11... Zn, Ni, Cd, Co are above in the negative potential...while Cu, Ag, Iodine and Iodate are below...

Cr(3+) and Cr(2+) seems to be on the safe side!




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[*] posted on 27-8-2013 at 06:00


Quote: Originally posted by PHILOU Zrealone  
Quote: Originally posted by papaya  
While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're instable or just no information?


The facts are that...
Zn nitrate forms a stable hydrazine complex
Ni (II) nitrate forms a stable hydrazine complex
Cd(II) nitrate forms a stable hydrazine complex
Co (II) nitrate forms a stable hydrazine complex
But...
Cu (II) nitrate forms an unstable hydrazine complex
Hydrazine and iodine or iodate are uncompatible...
Silver nitrate is unstable towards hydrazine...

So watching closely to the oxydoredox potential table
There must be an electrochemical explanation to this...
See hydrazine at potential at +0,11... Zn, Ni, Cd, Co are above in the negative potential...while Cu, Ag, Iodine and Iodate are below...

Cr(3+) and Cr(2+) seems to be on the safe side!


Well, once I tried to mix dilute Cr(NO3)3 + HNO3 solution with 50% hydrazine hydrate (few ml scale) and immediately obtained green precipitate which didn't burn and actually was metal hydroxide. However supernatant liquid turned into pink color which indicate something more interesting happened there besides that classical acid-base reaction. There was no formation of gas observed, so hopefully no worries about hydrazine decomposition. I didn't investigate it further because I have no source of decent quality chromium nitrate (pure solid salt), perhaps with a proper synthesis method this is doable. It may be fun for anyone here to try and report results and properties here for a first time before it get's published in academic journals (if it's really new)!
Also as there are 3 nitrate anions - more oxygen is available and it must be worth to try to prepare some (insoluble) complex with organics like acetonitrile, real pain is that many of these things may be soluble in water and require anhydrous conditions (as well as anhydrous chromium salt).
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[*] posted on 26-9-2013 at 13:31


Hi, a long thread so I might miss something - did anyone actually try to synthesize bis- nickel hydrazine azide, that is mentioned on p.13 here? How stable is it (to storage, humidity, etc.), ? Is it a "real" primary with a short DDT, or merely deflagrates/explodes? It's characterized as even less sensitive than tris- hydrazine nickel nitrate in Ilyushin's paper attached there, which is counter-intuitive (azide!). What about other azide complexes(Zn, Co,..) - was any tried here? Thanks.
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[*] posted on 26-9-2013 at 13:53


Quote: Originally posted by papaya  

Well, once I tried to mix dilute Cr(NO3)3 + HNO3 solution with 50% hydrazine hydrate (few ml scale) and immediately obtained green precipitate which didn't burn and actually was metal hydroxide. However supernatant liquid turned into pink color which indicate something more interesting happened there besides that classical acid-base reaction. There was no formation of gas observed, so hopefully no worries about hydrazine decomposition. I didn't investigate it further because I have no source of decent quality chromium nitrate (pure solid salt), perhaps with a proper synthesis method this is doable. It may be fun for anyone here to try and report results and properties here for a first time before it get's published in academic journals (if it's really new)!


Chromium(III) is a very non-labile ion. Once you've got [Cr(H2O)6]3+ in solution, the water ligands don't really want to come off very rapidly. If you let your solution mixture of chromium(III) nitrate and hydrazine stand for extended periods of time, you might form the complex.

If the solution is basic, that can speed it up (a base can catalyze it by forming a hydroxy complex, which is more labile), or you can sometimes catalyze it by reducing chromium(III) to chromium(II), which is much more labile.




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[*] posted on 26-9-2013 at 21:36


Thanks Draconic, so perhaps I had to keep that Cr(OH)3 formed in contact with solution for a long time until it converts to the desired product.
And what about bis- nickel hydrazinium azide ?
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[*] posted on 27-9-2013 at 10:10


Nickel(II) is quite labile- if it forms, it should form quickly.

I'm not sure how well azide works as a ligand, though- I don't have much experience with azides.




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[*] posted on 27-9-2013 at 10:14


Quote: Originally posted by AndersHoveland  

Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:

[(CH3)3N]3Ni+1(N3)3 • (ClO4)

The nickel center can only complex to 6 ligands, so that would leave a +1 ionic charge, so that perchlorate could be part of the complex salt also.

The electronic configuration of the nickel in this proposed compound would correspond to the nickel complex NiF62−, which has been described in the literature.

It could perhaps be prepared by reacting nickel(II) perchlorate with trimethylamine in excess hydrazoic acid.

[Edited on 17-3-2013 by AndersHoveland]


Sorry, but that's not going to work. Azide is an anionic ligand. To get [NiL3(N3)3]ClO4 (where L is a neutral ligand, such as ammonia or trimethylamine), you would have to have nickel in the +4 oxidation state, which is not preferred for nickel.




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[*] posted on 27-9-2013 at 10:24


http://www.tandfonline.com/doi/abs/10.1080/00945719608004763...
This might help if somebody has access...
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[*] posted on 29-9-2013 at 12:51


Thanks to Dany for the following article attached

Synthesis and Characterization of Some Cobalt(II), Nickel(II), Zinc(II) and Cadmium(II) Hydrazine Azides

K. K. Naranga, M. K. Singh (Mrs), K. B. Singh & R. A. Lal

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry
Volume 26, Issue 4, 1996, pages 573-589

Also attached is a related article of interest





Attachment: Metal Hydrazine azide complexe.pdf (508kB)
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Attachment: Hydrazine complexes of transition metals as explosives chemik_2011_65_1_24-27.pdf (193kB)
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[*] posted on 6-10-2013 at 13:51


Lately I managed to prepare and test some 0.2-0.3g of Ni[N2H4]2(N3)2 complex - it's a very fine light blue powder, that readily catches fire (flashes) when exposed to fire, I didn't notice it to be highly sensitive and can be handled without too much risk in my opinion (was a small quantity and I never tried to see how it behaves under different mechanical stimuli). However that 0.2g did NOT detonate when confined(slightly hand-pressed) into soft PVC tube having about 4mm of internal diameter and 1mm of wall thickness and lit from open side. So not a first class primary :P
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[*] posted on 14-12-2013 at 14:46


Quote: Originally posted by AndersHoveland  
Perchlorate complex salts of hydrazine are dangerously friction sensitive. Hydroxylamine perchlorate is very sensitive, having a drop height value of only 2cm.


Can I have a reference for the 2cm drop height value ?

That sounds very extreme! I've never seen a explosive with an positive OB of +42% can have such a sensitivity.
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[*] posted on 14-12-2013 at 14:58


Quote: Originally posted by Rosco Bodine  


franklyn mentions that carbohydrazide is also known as diaminourea ( DAU )
http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...




Di-dinitramide salt of this also seems to be interesting derivative.

[Edited on 14-12-2013 by DubaiAmateurRocketry]
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[*] posted on 5-2-2014 at 22:21


Hydrazine complexes of transition metals as prospective explosives

www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf

Coordination explosives

www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf

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[*] posted on 6-2-2014 at 10:35


Quote: Originally posted by franklyn  
Hydrazine complexes of transition metals as prospective explosives

www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf

Coordination explosives

www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf



Here attached is the second linked file and the first is a few posts above.



Attachment: chemik_01_2010_023_024.pdf (173kB)
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