Density functional theory (DFT) calculations were carried outto study the reaction mechanism of the first transmetalation oforganosilanes to gold as a cheap fluoride-free process. The versatilegold(I) complex [Au(OH)(IPr)] permits very straightforwardaccess to a series of aryl-, vinyl-, and alkylgold silanolatesby reaction with the appropriate silane reagent. These silanolatecompounds are key intermediates in a fluoride-free processthat results in the net transmetalation of organosilanes togold, rather than the classic activation of silanes as silicatesusing external fluoride sources. However, here we proposethat the gold silanolate is not the active species (as proposedduring experimental studies) but is, in fact, a resting stateduring the transmetalation process, as a concerted step is preferred
展开▼