X-ray Crystal Structures and the Facile Oxidative (Au−C) Cleavage of the Dimethylaurate(I) and Tetramethylaurate(III) Homologues

Authors

Dunming Zhu, University of Houston
Sergey V. Lindeman, Marquette UniversityFollow
Jay K. Kochi, University of Houston

Document Type

Article

Language

eng

Publication Date

1999

Publisher

American Chemical Society

Source Publication

Organometallics

Source ISSN

0276-7333

Abstract

Dimethylaurate(I) has been prepared as the crystalline tetrabutylammonium salt for comparison with the known tetramethylaurate(III) analogue. The linear structure of dimethylaurate(I) and the square-planar structure of tetramethylaurate(III) have both been confirmed by X-ray crystallography. One-electron oxidation of dimethylaurate(I) by either ferrocenium or arenediazonium cations produces the metastable dimethylgold(II) intermediate, which can be trapped as the paramagnetic 9,10-phenanthrenequinone (PQ) adduct. Otherwise, dimethylgold(II) is subject to rapid reductive elimination of ethane and affords metallic gold (mirror). The analogous oxidation of tetramethylaurate(III) by ferrocenium, arenediazonium, or nitrosonium cations also proceeds via electron transfer to generate the putative tetramethylgold(IV) intermediate. The highly unstable (CH₃)₄Au^IV spontaneously undergoes homolytic cleavage to produce methyl radical and the coordinately unsaturated trimethylgold(III), which can be intercepted by added triphenylphosphine to afford Me₃Au^IIIPPh₃.

Comments

Accepted version. Organometallics, Vol. 18, No. 11 (1999): 2241-2248. DOI. © 1999 American Chemical Society. Used with permission.

Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.

Recommended Citation

Zhu, Dunming; Lindeman, Sergey V.; and Kochi, Jay K., "X-ray Crystal Structures and the Facile Oxidative (Au−C) Cleavage of the Dimethylaurate(I) and Tetramethylaurate(III) Homologues" (1999). Chemistry Faculty Research and Publications. 692.
https://epublications.marquette.edu/chem_fac/692