56247-40-6Relevant articles and documents
Hidden Bronsted acid catalysis: Pathways of accidental or deliberate generation of triflic acid from metal triflates
Dang, Tuan Thanh,Boeck, Florian,Hintermann, Lukas
, p. 9353 - 9361 (2011)
The generation of a hidden Bronsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF3SO3H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl2/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Bronsted acid catalyst useful for mechanistic control experiments or for synthetic applications.
Effect of solvent and ancillary ligands on the catalytic H/D exchange reactivity of Cp IrIII(L) complexes
Lehman, Matthew C.,Gary, J. Brannon,Boyle, Paul D.,Sanford, Melanie S.,Ison, Elon A.
, p. 2304 - 2310 (2013/10/22)
The reactivity of a series of Cp*lIrIII(L) complexes that contain a diverse set of ancillary ligands, L, (L = PMe3, N-heterocyclic carbene, NHC = 1,3-dimethylimidazol-2-ylidene, aqua, 4-t-butylpyridine, and 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate) has been examined in catalytic H/D exchange reactions between C6H6 and a series of deuterated solvents (methanol-d 4, acetic acid-d4, and trifluoroacetic acid-d 1). These studies demonstrate that (1) the mechanism of catalytic H/D exchange is significantly influenced by the nature of the solvent; (2) electron-donating ligands (PMe3, NHC) promote the formation of Ir hydrides in methanol-d4, and these are critical intermediates in catalytic H/D exchange processes; and (3) weak/poorly donating ligands (4-t-butylpyridine, 4-(2,4,6-tris-(4-t-butylphenyl)pyridinium)pyridine tetrafluoroborate and aqua) can support efficient H/D exchange catalysis in acetic acid-d4.
