Gas phase synthesis and reactivity of dimethylaurate

A combination of multistage mass spectrometry experiments and DFT calculations were used to examine the synthesis and reactivity of dimethylaurate. Collision induced dissociation (CID) of (CH(3)CO(2))(4)Au(-) proceeded via reductive elimination of acetylperoxide to yield the diacetate CH(3)CO(2)AuO(2)CCH(3)(-), which in turn underwent sequential CID decarboxylation reactions to yield the organoaurates CH(3)CO(2)AuCH(3)(-) and CH(3)AuCH(3)(-). The unimolecular chemistry of the dimethylaurate proceeds via a combination of bond homolysis to yield the methyl aurate radical anion CH(3)Au (-) as well as formation of the gold dihydride HAuH(-). DFT calculations reveal that the latter anion is formed via a 1,2-dyotropic rearrangement to yield the isomer CH(3)CH(2)AuH(-), followed by a beta-hydride elimination reaction. Ion-molecule reactions of CH(3)AuCH(3)(-) with methyl iodide did not yield any products even at relatively high concentrations of the neutral substrate and longer reaction times, indicating a reaction efficiency of less than 1 in 20 000 collisions. DFT calculations were carried out on two different potential energy surfaces (PES) for the reaction of CH(3)AuCH(3)(-) with CH(3)I: (i) an S(N)2 mechanism proceeding via a side-on transition state; and (ii) a stepwise mechanism proceeding via oxidative addition followed by reductive elimination. Both pathways have significant endothermic barriers, consistent with the lack of C-C bond coupling products being formed in the experiments. Finally, the reactivity of CH(3)AuCH(3)(-) is compared to the previously studied CH(3)AgCH(3)(-) and CH(3)CuCH(3)(-), as well as condensed phase studies on dimethylaurate salts.