14996-98-6Relevant articles and documents
Photoswitchable hydride transfer from iridium to 1-methylnicotinamide rationalized by thermochemical cycles
Barrett, Seth M.,Pitman, Catherine L.,Walden, Andrew G.,Miller, Alexander J. M.
, p. 14718 - 14721 (2014)
Visible light-triggered hydride transfer from [CpIr(bpy)(H)]+ (1) to organic acids and 1-methylnicotinamide (MNA+) is reported (Cp = pentamethylcyclopentadienyl; bpy = 2,2′-bipyridine). A new thermochemical cycle for determining excited-state hydride donor ability (hydricity) predicted that 1 would be an incredibly potent photohydride in acetonitrile. Phototriggered H2 release was indeed observed from 1 in the presence of various organic acids, providing experimental evidence for an increase in hydricity of at least 18 kcal/mol in the excited state. The rate and product selectivity of hydride transfer to MNA+ are photoswitchable: 1,4-dihydro-1-methylnicotinamide forms slowly in the dark but rapidly under illumination, and photolysis can also produce doubly reduced 1,4,5,6-tetrahydro-1-methylnicotinamide.
