Gas phase synthesis and reactivity of dimethylaurate.

Dalton transactions (Cambridge, England : 2003) (2010-08-18)
Nicole J Rijs, Gustavo B Sanvido, George N Khairallah, Richard A J O'Hair
ABSTRACT

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.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Iodomethane, purum, ≥99.0% (GC)
Sigma-Aldrich
Iodomethane, contains copper as stabilizer, ReagentPlus®, 99%
Sigma-Aldrich
Iodomethane, contains copper as stabilizer, ReagentPlus®, 99.5%
Sigma-Aldrich
Iodomethane-d3, ≥99.5 atom % D, ≥99% (CP), contains copper as stabilizer
Sigma-Aldrich
Iodomethane solution, 2.0 M in tert-butyl methyl ether, contains copper as stabilizer
Sigma-Aldrich
Iodomethane-13C, 99 atom % 13C, 99% (CP), contains copper as stabilizer
Supelco
Iodomethane solution, certified reference material, 2000 μg/mL in methanol: water (4:1)