Tetrabutylammonium decatungstate photocatalysis is effective for the C-H activation of alkanes, aldehydes, ethers and amides and the alkylation of alkenes occurs effectively by merely exposing the solution to the sun in a glass vessel on a window ledge (up to 10 g per dm(2) in a few days).
Photocatalytic reactions have been defined as those processes that require both a (not consumed) catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal) equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction… (More)
Steady-state irradiation in neat acetonitrile of some aromatic nitriles, imides and esters (10(-5)-10(-3) M solution) in the presence of tertiary amines allowed the accumulation of the corresponding radical anions, up to quantitative yield for polysubstituted benzenes and partially with naphthalene and anthracene derivatives. The condition for such an… (More)
The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly)… (More)
UV absorption spectra of the Lindqvist polyoxometalate [W(6)O(19)](2-) were predicted by relativistic time-dependent density functional theory with several combinations of density functional and basis set. Hybrid functionals with frozen-core Slater basis sets were found to provide the best agreement with experiment while keeping reasonable computational… (More)
Irradiation of electron-donating substituted phenyl halides (fluorides and chlorides) or esters (mesylates, triflates and phosphates) in aqueous MeCN in the presence of KCN gives the corresponding benzonitriles in 48 to 100% yield through an ArSN1 reaction with the intermediacy of a triplet phenyl cation.
The photochemistry of the pyrazolo[1,2-a]benzotriazole 1b and its dimethyl derivative 1c was studied in argon matrices at 12 K and in solution at 190 K. On irradiation at 365 nm, 1b and 1e undergo ring closure to yield the triazasemibullvalenes 2b and 2c, respectively, which were identified unambiguously by NMR and IR spectroscopy. This novel type of… (More)