Astrochemistry of Magnesium Cations with Hydrogen Cyanide and Cyanoacetylene: Possible Formation of Cyclic Tetramers of Cyanoacetylene

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Molecular And Chemical Processes And Interactions, Astrobiology And Astrochemistry Of The Solar System And Interplanetary Space, Chemical Reactions, Energy Disposal, And Angular Distribution, As Studied By Atomic And Molecular Beams, Electron-Ion Recombination And Electron Attachment, Titan

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Laboratory measurements with the SIFT technique have shown that magnesium radical cations in a helium bath gas at 0.35 Torr and 294 K are unreactive with hydrogen cyanide but initiate a chemical sequence in cyanoacetylene that leads to the formation of Mg(HC3N)n+• cluster ions with n up to 7. Rate-coefficient measurements for sequential addition of cyanoacetylene to Mg+• indicate an extraordinary pattern in alternating chemical reactivity while multiple-collision induced dissociation experiments revealed an extraordinary stability for the Mg(HC3N)4+• cluster radical cation. Molecular orbital calculations with density functional theory (DFT) have provided structures and energies for the observed Mg(HC3N)1-4+• cations. These calculations indicate that the path of formation of Mg(HC3N)4+• appears to involve ligand-ligand interactions mediated by Mg+• to form 2,4,6,8-tetracyanosemibullvalene-Mg+• or 1,2,5,6-tetracyano-1,3,5,7-cyclooctatetraene-Mg+• cations. A case is made for the formation of similar complex organomagnesium ions in the upper atmosphere of Titan where subsequent electron-ion recombination may produce cyano derivatives of large unsaturated hydrocarbons. In contrast, circumstellar environments with their much higher content of free electrons seem less likely to give rise to such chemistry.

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