抄録
a) When Mercarbide and Mercuroform are warmed at 50-60° for 80 hrs in etherial solution of ethyl iodide, the former changes to Iodomercuroform HC≡(HgI)3 and the latter to Mercuroform diiodide.
HC ??
b) By immersion of Mercarbide-chloride, Mercuroform-dichloride and Chloromercuro-form in ammoniacal water saturated with ammonium chloride, ammine compounds of respective chloride (-Hg- ?? )3, HC ?? and HC≡[Hg(NH3)Cl]3 are formed as sparingly soluble gray white amorphous bodies.
c) Mercarbide-Sulfate (-HG- ?? )3=C3H3O3Hg9(HSO4)3, when immersed in KCl (and KBr) solution for 5 hrs at 80° liberates two of HSO4-group as SO411 to be dissolved in the solution and externally applied halogen ions take the place to form HgX-group. At the same time, an oxygen atom of oxide-linkage separates out from heteroring system leaving behind a chain structural molecule and two more halogen atoms combine to Hg-atom bonded on ends of the chain newly formed. Throughout these reaction sequence one of Hg(HSO4)-group remains unchanged.
(HSO4)-Hg- ??
→(HSO4)-Hg- ??
→(HSO4)-Hg- ??
C3H3O3Hg9(HSO4)3+4KX→C3H3O2X4Hg9(HSO4)+2K2SO4+H2O
Deniges' Substance, Formyl derivative of Mercarbide-Sulfate. (-HG- ?? )3=C6H3O6Hg9(HSO4)3 behaves similarly as above in anion exchange reaction with KCl (KBr) to form C6H3O5Cl4Hg9(HSO4) and C6H3O5Br4Hg9(HSO4) respectively as the end products
(HSO4-Hg- ?? [R=CHO]
Mercarbide (-Hg- ?? )3=C3H3O3Hg9(OH)3. In the old days, anion exchange reactions of Mercarbide in KBr (KCl) solution were reported by K. A. Hofmann. Since the group (HO)-Hg- in Mercarbide molecule ought to be corresponding to (HSO4)-Hg-group in molecule of Mercarbide-Sulfate, the end products from Mercarbide should be C3H3O2X4Hg9(OH). (HO)-Hg- ?? The analytical data of these end products reffered in Hofmann's past report agreed prefectly with above conception.
d) Mercuroform: Basing on various facts related to anion exchange reactions of Mercuroform and its salt, it is surmised that the structure of these substances might be dimer of Methanoxy trimercarbide.
??
Such a heterocyclic system should be much more stable than that of Methanoxytrimercarbide and a little labile than that of Mercarbide.
Though it is quite rational to think the structure of Methanoxytrimercarbide HC ?? to be prototypical form for the substances of this series, it seems rather doubtful whether such a substance could be actual molecule of Mercuroform or not.
