Observing Initial Steps in Gold-Catalyzed Alkyne Transformations by Utilizing Bodipy-Tagged Phosphine-Gold Complexes.

The Pd-catalyzed reactions of 3-chloro-bodipy with R2 PH (R=Ph, Cy) provide nonfluorescent bodipy-phosphines 3-PR2 -bodipy 3 a (R=Ph) and 3 b (R=Cy; quantum yield Φ<0.001). Metal complexes such as [AgCl(3 b)] and [AuCl(3 b)] were prepared and shown to display much higher fluorescence (Φ=0.073 and 0.096). In the gold complexes, the level of fluorescence was found to be qualitatively correlated with the electron density at gold. Consequently, the fluorescence brightness of [AuCl(3 b)] increases when the chloro ligand is replaced by a weakly coordinating anion, whereas upon formation of the electron-rich complex [Au(SR)(3 b)] the fluorescence is almost quenched. Related reactions of [AuCl(3 b)] with [Ag]ONf)] (Nf= nonaflate) and phenyl acetylenes enable the tracking of initial steps in gold-catalyzed reactions by using fluorescence spectroscopy. Treatment of [AuCl(3 b)] with [Ag(ONf)] gave the respective [Au(ONf)(3 b)] only when employing more than 2.5 equivalents of silver salt. The reaction of the "cationic" gold complex with phenyl acetylenes leads to the formation of the respective dinuclear cationic [{(3 b)Au}2 (CCPh)](+) and an increase in the level of fluorescence. The rate of the reaction of [Au(ONf)(3 b)] with PhCCH depends on the amount of silver salt in the reaction mixture; a large excess of silver salt accelerates this transformation. In situ fluorescence spectroscopy thus provides valuable information on the association of gold complexes with acetylenes.