Solid-state and dynamic solution behavior of a cationic, two-coordinate gold(I) π-allene complex
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2010-10-11
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Abstract
The cationic gold π-allene complex {[P(t-Bu)2o-biphenyl] Au[η2-H2C=C=C(CH3)2]} +SbF6- was isolated in 98% yield from reaction of 3-methyl-1,2-butadiene with a mixture of [P(t-Bu)2o-biphenyl]AuCl and AgSbF6 and was characterized by X-ray crystallography and variable-temperature NMR spectroscopy. These studies revealed preferential binding of gold to the less substituted C=C bond of the allene in both the solid state and solution and also revealed fluxional behavior consistent with π-face exchange of the allene ligand via an η1-C2 allene intermediate or transition state. © 2010 American Chemical Society.
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Brown, TJ, A Sugie, MG Dickens and RA Widenhoefer (2010). Solid-state and dynamic solution behavior of a cationic, two-coordinate gold(I) π-allene complex. Organometallics, 29(19). pp. 4207–4209. 10.1021/om100688t Retrieved from https://hdl.handle.net/10161/4112.
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Ross A. Widenhoefer
Research in the Widenhoefer group is directed toward the development and mechanistic analysis of new organotransition metal-catalyzed transformations for application in the synthesis of functionalized organic molecules. In particular, our group has a long-standing interest in the functionalization of C–C multiple bonds with carbon and heteroatom nucleophiles catalyzed by electrophilic late transition metal complexes, with a recent focus on the synthetic and mechanistic aspect of gold(I) pi-activation catalysis. Current areas of inquiry include the following:
- Gold(I) and Pt(II)-catalyzed hydroamination of alkenes an allenes.
- Gold(I)-catalyzed dehydrative amination of underivatized allylic alcohols.
- Synthesis and study of cationic, two-coordinate gold pi-complexes.
- Evaluating the role of bis(gold) complexes in gold pi-activation catalysis.
More detailed descriptions of these research projects can be found at our group web page.
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