Oxidative addition of a tungsten π-base into O-H, N-H, C-H, and C-F bonds

INOR 804

Kevin D. Welch, kdw9e@virginia.edu, Weijun Liu, and W Dean Harman. Department of Chemistry, University of Virginia, Charlottesville, VA 22904
A series of transition metal π-bases has been successfully developed as dearomatization agents for a broad range of arenes and aromatic heterocycles through dihapto coordination. As the electron-richness of these metal complexes is increased, there is a greater propensity for oxidative addition of the metal into O-H, N-H, and C-H bonds of the η2-coordinated ligand despite the presence of a rigid, tridentate Tp ligand. Unlike the less electron-rich {Os(NH3)5}2+ and {TpRe(CO)(N-methylimidazole)} dearomatization agents, the {TpW(NO)(PMe3)} π-base activates O-H and N-H bonds resulting in tungsten hydrides that are isolated as stable seven-coordinate complexes. Aryl C-H activation has been observed to be reversible for these complexes. The {TpW(NO)(PMe3)} fragment also activates C-F bonds in a similar manner to give analogous seven-coordinate complexes.
 

Organometallics
7:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006