38574-12-8Relevant academic research and scientific papers
Arene-mercury complexes stabilized by aluminum and gallium chloride: Catalysts for H/D exchange of aromatic compounds
Borovik, Alexander S.,Barron, Andrew R.
, p. 3743 - 3748 (2002)
Dissolution of Hg(arene)2(MCI4)2 [arene = C6H5Me, C6H5Et, o-C6H4Me2, C6H3-1,2,3-Me3; M = Al, Ga] in C6D6 results in a rapid H/D exchange and the formation of the appropriate dn-arene and C6D5H. H/D exchange is also observed between C6D6 and the liquid clathrate ionic complexes, [Hg(arene)2(MCl4)]-[MCl4], formed by dissolution of HgCl2 and MCl3 in C6H6, m-C6H4Me2, or p-C6H4Me2. The H/D exchange reaction is found to be catalytic with respect to Hg(arene)2(MCl4)2 and independent of the initial arene ligand. Reaction of a 1:1 ratio Of C6H5Me and C6D6 with 6H5Me)2(MCl4)2 results in an equilibrium mixture of all isotopic isomers: C6H5-xDxMe and C6D6-xHx (x = 0-5). DFT calculations on the model system, Hg(C6H6)2(AlCl4)2 and [Hg(C6H6)2(AlCl4)+, show that the charge on the carbon and proton associated with the shortest Hg···C interactions is significantly higher than that on uncomplexed benzene or HgCl2(C6H6)2. The protonation of benzene by either Hg(C6H6)2(AlCl4)2 or [Hg(C6H6)2(AlCl4)]+ was calculated to be thermodynamically favored in comparison to protonation of benzene by HO2CCF3, a known catalyst for arene H/D exchange. Arene exchange and intramolecular hydrogen transfer reactions are also investigated by DFT calculations.
