Issue 37, 2010

Gas phase synthesis and reactivity of dimethylaurate

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 [(CH3CO2)4Au] proceeded via reductive elimination of acetylperoxide to yield the diacetate [CH3CO2AuO2CCH3], which in turn underwent sequential CID decarboxylation reactions to yield the organoaurates [CH3CO2AuCH3] and [CH3AuCH3]. The unimolecular chemistry of the dimethylaurate proceeds via a combination of bond homolysis to yield the methyl aurate radical anion [CH3Au]˙ 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 [CH3CH2AuH], followed by a β-hydride elimination reaction. Ion-molecule reactions of [CH3AuCH3] 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 [CH3AuCH3] with CH3I: (i) an SN2 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 [CH3AuCH3] is compared to the previously studied [CH3AgCH3] and [CH3CuCH3], as well as condensed phase studies on dimethylaurate salts.

Graphical abstract: Gas phase synthesis and reactivity of dimethylaurate

Supplementary files

Article information

Article type
Paper
Submitted
20 May 2010
Accepted
15 Jul 2010
First published
12 Aug 2010

Dalton Trans., 2010,39, 8655-8662

Gas phase synthesis and reactivity of dimethylaurate

N. J. Rijs, G. B. Sanvido, G. N. Khairallah and R. A. J. O'Hair, Dalton Trans., 2010, 39, 8655 DOI: 10.1039/C0DT00508H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements