bismuthate
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Pnictogen hydride acid-base chemistry
Phosphonium salts are very underresearched. Does anybody have experience with them? So anyway I was thinking of making PH4Cl. could this be done by
the gas phase reaction of PH3 and HCl at rt? Also could PH4+ (or PH2-) salts react with Sb to yield elemental P?
[Edited on 11-12-2013 by bismuthate]
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blogfast25
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No, they're not. But they're hard to produce at the home level because phosphine is so toxic and inflammable.
Sb? Huh? 
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bismuthate
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Sb as in antimony. I was wondering if it could replace P in PH4+ or PH2- containing compounds.
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DraconicAcid
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Single replacement reactions occur in simple ions- you are not going to get a reaction of the form 4 PH3 + 4 Sb -> 4 SbH3 +
P4.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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blogfast25
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Yeah, I know what Sb stands for  .
You mean 'replace' or 'displace'? Stibine does exist, as does AsH3 and BiH3. As one goes down the series these compounds are progressively harder to
protonate. Hence AsH3 already requires superacids to get AsH<sub>4</sub><sup>+</sup> cations.
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bismuthate
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Ahh sorry.
Well has anyone dealt with phosphonium ions or PH2- (no idea what they're actually called)?
I know that quite a few people here do deal with strong toxins.
Yeah I meant displace. Funny you metioned SbH3 since that is actually the thing that made me make this thread. (I was going to be using SbH3 to make
NaSbH2 and I saw the other XH4 ions (x standing for a pnictogen (hey I used a parenthese in a parenthese)) and they where realy interesting (I wonder
what it would take to protonate BiH3(I would love to have a bismuthonium salt))) (Oh! Well that was a hopelessly jumbled pile of parentheses )
[Edited on 11-12-2013 by bismuthate]
[Edited on 11-12-2013 by bismuthate]
[Edited on 11-12-2013 by bismuthate]
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DraconicAcid
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I've never worked with either, but I used to work with a guy who made KPPh2 as an intermediate in an organic synthesis (he got it by
reacting thriphenylphosphine with potassium in some ether; he was making a fancy ligand).
Cotton & Wilkinson (4th ed) state that phosphonium chloride and bromide will dissociate into phosphine and hydrogen halide below 0oC; the iodide
is more stable. Water will completely hydrolyze phosphonium salts. It does not mention analogues of the amide anion. Greenwood & Earnshaw
mention it, but do not name it.
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bismuthate
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Well I know that
NaNH2+AsH3==>NaAsH2+NH3 so I can predict that phosphine will behave the same way.
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DraconicAcid
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G&E point out that phosphine will dissolve in liquid ammonia to give ammonium whatever-you-call-that-anion. (That's G&E's Chemistry of the
Elements, 2nd Ed) So you don't need to use the amide, just the anhydrous liquid.
Probably "ammonium dihydrogen phosphide".
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bismuthate
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i wonder if bubbling PH3 through liquid SbH3 would yield PH4SbH2. I would try that if it weren't so bloody dangerous.
By the way I believe that the title should be changed to pnictogen hydride chemistry.
[Edited on 11-12-2013 by bismuthate]
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DraconicAcid
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Quote: Originally posted by bismuthate  | i wonder if bubbling PH3 through liquid SbH3 would yield PH4SbH2. I would try that if it weren't so bloody dangerous.
By the way I believe that the title should be changed to pnictogen hydride chemistry.
[Edited on 11-12-2013 by bismuthate] |
I doubt it- phosphine's a lousy base. But bubbling ammonia through liquid stibnine should work.
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bismuthate
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Good point however I bet H2SO4 could protonate it.
I may decide to make NH4SbH2 like that (I planned to react it wit Li).
I also wonder if SbH4 salts are possible with weak anions (carbicde, azide, ect) through metaphisis reations.
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DraconicAcid
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| Quote: Originally posted by bismuthate | Good point however I bet H2SO4 could protonate it.
I may decide to make NH4SbH2 like that (I planned to react it wit Li).
I also wonder if SbH4 salts are possible with weak anions (carbicde, azide, ect) through metaphisis reations. |
G&E say "there is little tendency to form the onium ions MH4+ analogous to MH4+. Hoever, very
recently the thermally unstable salts [AsH4][SbF6] (decomp. -40 oC), [AsH4][AsF6] (d. -75 oC) and
[SbH4][SbF6] (d. -70 oC) have been isolated as colourless air- and moisture-sensitive crystals."
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bismuthate
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Thats odd that it's so unstable as SbF6 is a rather strong anion.
I bet that an attempted metathesis reation with carbides or azides would just end in an explosion though
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blogfast25
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Well, you can't have one, so there
But preparing small amounts of BiH<sub>3</sub> isn't too hard, it's similar to Marsh for arsine. But it's very unstable... It's discovery
is famously linked to the discovery of a particular radio isotope (can't remember which one right now) at the dawn of age of nuclear physics.
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bismuthate
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biH3 could by prepare by the hydrolysis of bismuthides I believe.
Also I would hypothesize reacting ammonia with bismuthane gas would yield NH4BiH2. that would be a very interesting salt.
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bismuthate
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Would NH4PH2 further react with NH3 to yield (NH4)3P?
Also I would think that I would be able to react NH4SbH2 with PH4Cl to obtain PH4SbH2 I wonder how stable that is.
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DraconicAcid
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That would probably give you PH3 and SbH3.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Brain&Force
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Did my thread for uncharacterized compounds inspire this?
My internal etymology-man suggests phosphanide, arsanide, stibanide, and bismuthanide for the ions. I know the first two are correct; Google gives
relevant results fo the first two. (Perhaps it is phosphinide, arsinide and stibinide, derived from the gas names.)
This is my guess from the IUPAC name for SH-, sulfanide.
At the end of the day, simulating atoms doesn't beat working with the real things...
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bismuthate
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It is indeed phosphinide, Although if it were up to me I like the name phosphomide.
DraconicAcid, yes but at <0 temps would I would suspect that PH4SbH2 would form as an almost instantly decomposing intermediate.
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