Structure of a Reactive Gold Carbenoid

Authors


  • Generous financial support by the MPG and the Fonds der Chemischen Industrie is gratefully acknowledged. We thank J. Rust, E. Dreher, and Prof. C. W. Lehmann for solving the X-ray structure and W. Wisniewski and Dr. C. Farès for support with NMR analyses.

Abstract

A formal gold-for-chromium transmetalation allowed the gold carbenoid species [Cy3PAuCAr2]NTf2 (11) (Ar=pMeOC6H4-) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest Au[BOND]C double-bond character; rather, it is the organic ligand framework that is responsible for stabilizing this species by resonance delocalization of the accumulated positive charge. Because 11 is capable of cyclopropanating p-methoxystyrene even at low temperature, the discussion of its structure is deemed relevant for a better understanding of the mechanisms of π-acid catalysis in general.

Ancillary