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 tris(N,N-diethyldithiocarbamato)iron(III)
Abstract The photolysis of [Fe(Et2dtc)3], Et2dtc = diethyldithiocarbamate to yield [Fe(Et2dtc)2Cl] proceeds under 313 nm irradiation through a metal complex excited state, as expected. Under 254 nm irradiation, however, the dominant pathway is through a solvent-initiated reaction in which radicals formed after absorption of light by CHCl3 react thermally with [Fe(Et2dtc)3]. The initial rate varies linearly with the light intensity at 313 nm, but at 254 nm varies with the square root of the intensity.
Electronic Energy Levels in Hexahalotellurate (IV) Complexes
The electronic spectra of the octahedral Tecl_6^(2-) and TeBr+6^(2-) complexes are reported and assigned. 
The s → p transition a_(lg)σ^* → t_(lu)σ^* gives rise to three spin-allowed bands in TeCl_6^(2-) (32,880; 34,480; 35,680 cm^(-1)) and TeBr_6^(2-) (28,470; 29,730; 30,850 cm^(-1)). These data are taken as evidence that the excited singlet states are distorted to lower symmetry, probably C_(2v). The lowest allowed halide → Te(IV) charge transfer transitions are at 44,170 cm^(-1) and somewhat higher than 52,000 cm^(-1) in TeCl_6^(2-); analogous transitions appear at 37,000 and 42,600 cm^(-1) in TeBr_6^(2-). The observed spectral data indicate that the "inert" 5s^2 Te(IV) electrons, which reside in the a_(lg)σ^* level, are partially delocalized to the halide ligands.