Abstract
The metal oxide polymeric methyltrioxorhenium [(CH 3) x ReO 3] ∞ is a unique representative of a layered inherent-conducting organometallic polymer which adopts the structural motifs of classical perovskites in two dimensions (2D) in form of methyl-deficient, corner-sharing ReO 5(CH 3) octahedra. In order to improve the characteristics of polymeric methyltrioxorhenium with respect to its physical properties and potential usage as an inherent-conducting polymer we tried to optimise the synthetic routes of polymeric modifications of 1 to obtain a sintered ceramic material, denoted as ceramic MTO. Ceramic MTO formed in a solvent-free synthesis via auto-polymerisation and subsequent sintering processing displays clearly different mechanical and physical properties from polymeric MTO synthesised in aqueous solution. Ceramic MTO is shown to display activated Re C and Re O bonds relative to MTO. These electronic and structural characteristics of ceramic MTO are also reflected by a different chemical reactivity compared with its monomeric parent compound. First examples of the unprecedented reactivity of ceramic MTO in the field of amine oxidations are shown – results which warrant further exploitation.
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