42892-91-1Relevant academic research and scientific papers
Photochemistry of (μ-tetraphenylporphyrinato)bis[dicarbonylrhodium(I)] in benzene - carbon tetrachloride mixture. Formation of chloro(tetraphenylporphyrinato)carbonylrhodium(III)
Hoshino, Mikio,Yasufuku, Katsutoshi
, p. 4408 - 4410 (2008/10/08)
Photolysis of (μ-tetraphenylporphyrinato)bis[dicarbonylrhodium(I)] (TPP[RhI(CO)2]2) in a 5:1 mixture of benzene and carbon tetrachloride gives rise to the formation of chloro(tetraphenylporphyrinato)carbonylrhodium(III) (Cl(TPP)RhIII(CO)). The quantum yield (Φ) for the photodecomposition of TPP[RhI(CO)2]2 is markedly dependent on the excitation wavelength (λ): Φ = 0.075 ± 0.04, λ -4, λ > 420 nm. The laser photolysis studies of TPP[RhICO)2]2 using the second (532 nm) and the third (355 nm) harmonic of a Nd-YAG laser reveal that neither the lowest singlet nor the triplet state is responsible for the photodecomposition of TPP[RhI(CO)2]2. The homolysis of the Rh(I)-N bond in the higher excited singlet states of TPP[RhI(CO)2]2 is considered to result in the formation of a transient species, TPP-[RhII(CO)2]. The assumption that TPP[RhII(CO)2]2 abstracts a chlorine atom from carbon tetrachloride gives an interpretation for the formation of Cl(TPP)RhIII(CO): (TPP)RhII(CO)2 + CCl4 → Cl(TPP)RhIII(CO) + CO + CCl3.
