Photo Lewis acid generators: photorelease of B(C6F5)3 and applications to catalysisElectronic supplementary information (ESI) available: Additional experimental and spectroscopic details and crystallographic data for 3-Ph3S, and 7-Ph2I. CCDC 1415835 and 1415836. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/C5DT03008K

A series of molecules capable of releasing of the strong organometallic Lewis acid B(C 6 F 5 ) 3 upon exposure to 254 nm light have been developed. These photo Lewis acid generators (PhLAGs) can now serve as photoinitiators for several important B(C 6 F 5 ) 3 -catalyzed reactions. Herein is described the synthesis of the triphenylsulfonium and diphenyliodonium salts of carbamato- and hydridoborates, their establishment as PhLAGs, and studies aimed at defining the mechanism of borane release. Factors affecting these photolytic reactions and the application of this concept to photoinduced hydrosilylation reactions and construction of siloxane scaffolds are also discussed. A series of molecules capable of releasing of the strong organometallic Lewis acid B(C 6 F 5 ) 3 upon exposure to 254 nm light have been developed.