822341-31-1Relevant academic research and scientific papers
Organogermanium reactive intermediates. The direct detection and characterization of transient germylenes and digermenes in solution
Leigh, William J.,Harrington, Cameron R.,Vargas-Baca, Ignacio
, p. 16105 - 16116 (2004)
Diphenylgermylene (Ph2Ge) and its Ge=Ge doubly bonded dimer, tetraphenyldigermene (6a), have been characterized directly in solution for the first time by laser flash photolysis methods. The germylene is formed via (formal) cheletropic photocycloreversion of 3,4-dimethyl-1,1- diphenylgermacyclopent-3-ene (4a), which is shown to proceed in high chemical (>95%) and quantum yield (Φ = 0.62) by steady-state trapping experiments with methanol, acetic acid, isoprene, and triethylsilane. Flash photolysis of 4a in dry deoxygenated hexane at 23°C leads to the prompt formation of a transient assigned to Ph2Ge (∈max = 500 nm; ∈max = 1650 M-1 cm-1), which decays with second-order kinetics (τ ≈ 3 μs), with the concomitant growth of a second transient species that is assigned to digermene 6a (τ ≈ 40 μs; λmax = 440 nm). Analogous results are obtained from 1,1-dimesityl- and 1,1-dimethyl-3,4-dimethylgermacyclopent-3-ene (4b and 4c, respectively), which afford Mes2Ge (τ = 20 μs; λmax = 560 nm) and Me2Ge (τ ≈ 2 μs; λs; λmax = 480 nm), respectively, as well as the corresponding digermenes, tetramesityl- (6b; λmax = 410 nm) and tetramethyldigermene (6c; λmax = 370 nm). The results for the mesityl compound are compared to the analogous ones from laser flash photolysis of the known Mes2Ge/6b precursor, hexamesitylcyclotrigermane. The spectra of the three germylenes and two of the digermenes are in excellent agreement with calculated spectra, derived from time-dependent DFT calculations. Absolute rate constants for dimerization of Ph2Ge and Mes2Ge and for their reaction with n-butylamine and acetic acid in hexane at 23°C are also reported.
