The photolysis of dichlorotriphenylbismuth(V) in chloroform.
Under 254 nm irradiation in chloroform, Bi(C6H5)3Cl2 reacts to yield HBiCl4 and H2BiCl5, in contrast to its behavior in acetonitrile, in which bismuth metal appears to be the eventual product, unless anhydrous HCl is present, in which case H2BiCl5 is also formed. The photolysis in CHCl3 is not significantly solvent-initiated. The rate depends directly on the light intensity absorbed by the metal complex, and the quantum yield is 0.026. In CCl4 a portion of the reaction occurs through absorption of light by the solvent.
The Solvent‐Initiated Photochemistry of Tetrachloropalladate(II) in Chloroform
Under 254 nm irradiation in chloroform, [PdCl4]2− is protonated to H2PdCl4 by HCl, generated through absorption of light by CHCl3. This stands in contrast to the behavior of [PtCl4]2− and [Pt(bpy)Cl2], which undergo photooxidation under the same conditions.
The Reactions of Methyl Radicals in the Solid-, Liquid-, and Gas-Phase Photolysis of Dimethylmercury
The gas-phase photolysis of CD3COCD3 was investigated in the presence of CH3HgCH3 from 376 to 453 deg K. From the isotopic distributions of the methane and ethane fractions, evidence was obtained for the occurrence of the reaction: CD3 + CH3HgCH3 → CD3 HgCH3+ CH3 (Eact = 12.6 kcal/mole). The reaction is also postulated to occur in the liquid-phase photolysis of dimethylmercury. From the isotopic distribution of the ethane produced in the liquid- and solid-phase photolysis of CH3HgCH3-CD3HgCD3 mixtures, it was concluded that cage recombination of methyl radicals does take place. Contrary to previous conclusions, no evidence could be obtained for hot methyl radical effects in the liquid-phase photolysis of dimethylmercury.