Consequences of the Formation of an Organometallic Exciplex [Hg(η2-arene)] in Mercury-Photosensitized Reactions of Arenes: C−C, C−O, and C−N Bond Cleavage

Abstract

We have previously shown that mercury-photosensitized reactions give an unexpected C-C bond cleavage for PhCH{sub 2}-CH{sub 3} and related aromatic systems. In this paper we report further theoretical and experimental studies that demostrate the importance of organometallic intermediates of the type {sup 3}[Hg({eta}{sup 2}-ArR)] in this chemistry and suggest how the C-C cleavage reaction occurs. We also find that in addition to these C-C bond cleavage reactions, analogous C-O and C-N bond cleavages can also occur with the following preference order for bond cleavage: C-O > C-N > C-C. 18 refs., 3 figs., 7 tabs.