I want to perform a reaction, in which sodium metal should produce solvated electrons. But my limitations are that I cannot use Liquid Ammonia, Methylamine or Ethylamine etc. as solvent. Therefore, I need some reagent which can act both as basic solvent and also produce solvated electrons within the reaction.
Please suggest.
https://en.wikipedia.org/wiki/2.2.2-Cryptand
This compound was available commercially (Merck catalogue) and build complex with sodium : Na+ will included in cavity of cryptand, free electron is solvated with sodium atom and build sodium anion Na- ; complex is bronze-orange solid.
Second possible candidate is commercially available podand N(CH2CH2OCH2CH2OCH3)3 but more active metal should be used (K, Rb, Cs or better alloys with Na as "oxidant" - electron acceptor). In contrary to above mentioned reaction using amines as solvents (or its mixtures with ether-type solvents like triglym), this chemistry is very dangerous and need dry and inert atmosphere.
Less reactive are complexes of metals with aromatic hydrocarbons (naphthalene, anthracene etc). Sodium naphthalenide Na+ C10H8- (green in color) https://en.wikipedia.org/wiki/Sodium_naphthalenide is commercial reagent and is applied for tetrafluoroethylene etching in mild conditions . Electron is solvated by pi-system of such hydrocarbons.
Also check https://en.wikipedia.org/wiki/Birch_reduction
Dear Michael SIr,
Many thanks for the information. I would look up to HMPA as a solvent but many restrictions comes in the way before using HMPA. The most important is the Toxicity and Cost. Are there any other alternatives?
Thanks
Regards
Ph3P=O also can react in same manner, but is not dangerous. Problem is that so-named phosphyls and its carbon analogs - ketyls https://en.wikipedia.org/wiki/Ketyl are not real solution of alkali metals - reaction is irreversible in contrary to examples noted by me.
Solution of potassium metal in H2O (0.00001M) is also blue in color - it contain solvated electrons. But attempt to rise concentration to practically high values lead to reaction with water - with KOH as product. I hope that you feel difference in two types of solutions.
Dear Andrei Sir and Michael Sir,
Since, this area is very well demanding and necessary for future of non-aqueous solvents, therefore, as a student I wish to work in this field under your supervisions.
I request you for a positive reply for the collaborative work in this area of Chemistry.
Regards
Sachin
Brain-explosion facts are best means to activate dormant audience, Micha !
No, I have not publication in hand - it was in my memory since studentship after reading of textbook "Общая химия" ="Angewandte Chemie", 3-rd ed., Nekrasov B.V., 1973. Main material is supported with numerous examples but without citation unfortunately. You can read https://en.wikipedia.org/wiki/Solvated_electron - water and alcohols are also suitable for electrons solvation. Naturally, potassium solution noted by Nekrasov was made not in tap water - it was extremely purified H2O.
But you can try "modern" methods https://www.youtube.com/watch?v=aHkYw78Bvac - and publication DOI: 10.1002/anie.201605986 - German professor finaly know that was routine for Russian students in 1981 :-)
http://sci-hub.cc/10.1002/anie.201605986
https://www.youtube.com/watch?v=aHkYw78Bvac
https://www.youtube.com/watch?v=HvVUtpdK7xw
@Suchin
I remembered one unique solvent - Et2N-SO2-NEt2 - it is aprotic dipolar solvent that compartable with RLi and RMgHal. Maybe it can replace liquid cancer . Available in some catalogues and in reaction
Et2NH + SO2Cl2 ->(pentane, RT) ->Et2N-SO2-NEt2
DMI and DMPU are also good candidates to test, propylene carbonate in mix with DME is used in lithium butteries.
Beta-rays are pure sources of electrons in liquids -> suitable for fast preliminary screening of solvents by spectroscopical methods. Stability of materials in conditions of high-dose radiation was investigated during nuclear programs in many countries - maybe you can find something in open literature.
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