Photochemical reactivity of cis and trans(AupNBT)2: A role for gold-gold interactions?

INOR 208

Janet B. Foley, jfoley@bennington.edu, Division of Natural Sciences and Mathematics, Bennington College, Rte 67A, Bennington, VT 05201 and Angela Herring, Division of Natural Science and Mathematics, Bennington College, Rte 67A, Bennington, VT 05201.
An investigation into the effect of thiol ligands on the cis→trans isomerization of a series of dinuclear gold(I) complexes revealed an additional interesting photochemical process for the trans-(AupNBT)2dppee complex. [pNBT = para-nitrobenzenethiol, dppee = diphenylphosphinoethylene]. A crystal structure for the cis-(AupNBT)2dppee reveals a short intramolecular gold-gold distance (3.0037(3)Å) while the trans-(AupNBT)2dppee crystal is a dimer with intermolecular gold-gold distance of (3.1201(4)Å). The solid state trans-(AupNBT)2dppee luminesces orange under UV light.1H NMR and UV-visible studies suggest that the cis complex isomerizes to the trans which immediately undergoes further reaction. Characterization of the photoproduct is discussed as well as possible mechanisms. Ab initio calculations are used to interpret the results.
 

General Inorganic Chemistry
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007