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Coordination Compounds of Bismuth
In school I was getting some chemicals for my teacher and I found a relatively large reagent bottle of Bismuth (III) Nitrate Trihydrate and I was
wondering if I can prepare any interesting coordination compounds from it. I assume that Bismuth's coordination number is 6 but could it also be 4?
What can I make? I'll try somethig whenever I get some free time in class.
I think I've heard of the [BiCl4]- , and [BiCl6]-
This means I could synthesize such compounds as [Bi(NH3)4]+++ and the like. Does anyone have suggestions?
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JohnWW
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I do not think I have head of any such cationic complexes of Bi, or of similar metals like Sb, As, Pb, Sn, Te, or Po, although anionic complexes are
well-known. Unlike transition-metal cationic complexes, cations of these metals, which utilize vacancies in s and p orbitals (which vacancies are
fewer than, for example, alkaline earth cations such as Mg++), are too easily hydrolysed to neutral covalent compounds. You could try highly
sequestering ligands such as porphyrins and similar, EDTA, crown ethers, and crown thio-ethers.
If you have access to a Ra-Be neutron source, I suppose you could then use it to make your own Po-210, as used to kill Col. Litvinenko a few months
ago.
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12AX7
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Bismuth does like to make -yl sorts of ions, indication of the covalent oxygen-hungryness that tends to go with high valence elements at the extreme
ends of the 'table (compare: titanyl, vanadyl, etc.).
I wonder if you might convince it to hang out with other fellows. If there's a compound that's soluble in an organic solvent (like THF), it might
form different complexes. There's something similar, I want to say AlCl3, that's known to, when "dissolved in" (reacted with) water, of course forms
a hydrato- complex, but when dissolved in a polar organic solvent like THF, forms a complex, which can even then be dissolved in another solvent (like
benzene) and forms a "benzenated" (analogous to "hydrated") crystalline material with all this organic junk. Oh, maybe it was TiCl4? Oh- it was!
Tim
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not_important
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I don't think you can do much in aqueous solutions, Bi compounds tent to hydrolyze. There's a lot of work done on oxide complexes like the high
temperature superconductors and the non-linear optical crystals like BBO - bismuth triborate. And there is research done in non-aqueous solvents.
http://adsabs.harvard.edu/abs/2003JSSCh.176..127H
http://www.ingentaconnect.com/content/els/02775387/1998/0000...
http://journals.iucr.org/e/issues/2007/06/00/at2292/at2292su...
http://www.ingentaconnect.com/content/nrc/cjc/2003/00000081/...
http://adsabs.harvard.edu/abs/1989PhyC..157..515S
http://pubs.acs.org/cgi-bin/abstract.cgi/inocaj/2004/43/i10/...
http://www.chem.sc.edu/faculty/zurloye/52.pdf
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The_Davster
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You might try reducing it to the metal, which can then be used to make really nice crystals from a melt.
BiI3 and [BiI4]- are simple to make, I can dig out a procedure tomorrow if you are interested. You are not going to get much aqueous bismuth
chemistry, the stuff hydrolyses at every chance it gets.
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Nerro
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Bi can also form wade clusters. I've read about something like Bi<sub>5</sub><sup>2-</sup> before.
#261501 +(11351)- [X]
the \"bishop\" came to our church today
he was a fucken impostor
never once moved diagonally
courtesy of bash
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Chemophiliac
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The wade clusters and BiI3 and [BiI4]- sound cool! The_Davster, dig up those procedures! I want to try my hands at those syntheses. Maybe I can even
grow large crystals of the compounds when I'm done.
However, I did forget that Bismuth DOES have the bad habit of hydrolyzing in water to form like a bismuthyl ion BiO+ type of thing. I haven't had a
lot of chances to fool around with bismuth compounds, actually, this will be my first time doing anything with them. What type of solvents would be
good for working with bismuth compounds without risk of them complexing to the solvents themselfs? And additionally, maybe I'll observe Bi's behavior
in THF.
Ahhhghg! So many experiments, so little time...
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woelen
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Probably this is what you are looking for. Bismuth makes beautiful complexes with iodide, and one can also make the solid BiI3, as long as no chloride
is present. Work at very low pH, with nitric acid or sulphuric acid.
http://woelen.scheikunde.net/science/chem/exps/Bi+halogen/in...
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Mr. Wizard
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Not exactly on topic but an interesting compound or amalgam of Mercury is mentioned in "Giacomo Casanova The memoirs of Jacques Casanova de Seingalt"
I have never read about this anywhere else. Does anyone else know about it? It would imply the Bismuth plays some part in allowing the Lead and
Mercury to amalgamate more completely and stay in a liquid form.
http://etext.library.adelaide.edu.au/c/casanova/c33m/chapter...
"It is quite naturally and without any intention to deceive, that a young man accustomed to poverty, and ashamed of it when he speaks to a rich
stranger, boasts of his means—of his fortune. As I was talking with my new acquaintance, I recollected an amalgam of mercury with lead and bismuth,
by which the mercury increases one-fourth in weight. I said nothing, but I bethought myself that if the mystery should be unknown to the Greek I might
profit by it. I felt that some cunning was necessary, and that he would not care for my secret if I proposed to sell it to him without preparing the
way. The best plan was to astonish my man with the miracle of the augmentation of the mercury, treat it as a jest, and see what his intentions would
be."
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