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.
Rijs
Nicole J
NJ
School of Chemistry, The University of Melbourne, Victoria, 3010, Australia.
Sanvido
Gustavo B
GB
Khairallah
George N
GN
O'Hair
Richard A J
RA
D002264:Carboxylic Acids / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D005740:Gases / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D017612:Gold Compounds / Q000737:chemistry*; D006847:Hydrocarbons, Iodinated / Q000737:chemistry; D013058:Mass Spectrometry; D013816:Thermodynamics
D002264:Carboxylic Acids; D005740:Gases; D017612:Gold Compounds; D006847:Hydrocarbons, Iodinated; D006046:Gold; D003300:Copper; C014055:methyl iodide