Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 4, 2013
Previous Article Next Article

Gold–allenylidenes – an experimental and theoretical study

Author affiliations

Abstract

Herein we describe the isolation and characterisation of the first “gold–allenylidene” complexes [Au[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CR2]+ X (R = N(CH2)n, OMe; n = 3, 4; X = OTf) and present a bonding model for these species based on an experimental and theoretical analysis. Heteroatom stabilisation (oxygen and nitrogen donors) overpowers the ligand effect on gold and has a large impact on the distribution of electron density in the allenylidene fragment. The description of a gold-stabilised propargylic cation rather than a gold–vinylidene complex is favoured, clearly indicated by experimental and theoretical work. Removing this heteroatom stabilisation by means of a theoretical analysis shows that the choice of ligand can fine-tune the electronics ranging from a gold-stabilised carbocation towards a Au–allenylidene. This observation is in excellent agreement with the recent gold “carbene vs. carbocation” discussion and expands the understanding of Au–carbocation interactions to include gold–cumulene systems.

Graphical abstract: Gold–allenylidenes – an experimental and theoretical study

Back to tab navigation

Supplementary files

Article information


Submitted
14 Dec 2012
Accepted
16 Jan 2013
First published
17 Jan 2013

Chem. Sci., 2013,4, 1552-1559
Article type
Edge Article

Gold–allenylidenes – an experimental and theoretical study

M. M. Hansmann, F. Rominger<small xmlns="http://www.rsc.org/schema/rscart38"> <sup /> </small> and A. S. K. Hashmi, Chem. Sci., 2013, 4, 1552
DOI: 10.1039/C3SC22227F

Social activity

Search articles by author

Spotlight

Advertisements