Diphenylgermylene (Ph2Ge) and its Ge=Ge doubly bonded dinner, 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 (Phi = 0.62) by steady-state trapping experiments with methanol, acetic acid, isoprene, and triethylsilane. Flash photolysis of 4a in dry deoxygenated hexane at 23degreesC leads to the prompt formation of a transient assigned to Ph2Ge (Am = 500 nm; is an element of(max) = 1650 M-1 cm(-1)), which decays with second-order kinetics (tau approximate to 3 mus), with the concomitant growth of a second transient species that is assigned to cligermene 6a (tau approximate to 40 mus; lambda(max) = 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 Mes(2)Ge (tau approximate to 20 mus; lambda(max) = 560 nm) and Me2Ge (tau approximate to 2 mus; lambda(max) = 480 nm), respectively, as well as the corresponding digermenes, tetramesityl- (6b; lambda(max) = 410 nm) and tetramethy1cligermene (6c; lambda(max) = 370 nm). The results for the mesityl compound are compared to the analogous ones from laser flash photolysis of the known Mes(2)Ge/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 Mes(2)Ge and for their reaction with n-butylamine and acetic acid in hexane at 23degreesC are also reported.