화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.120, No.6, 1172-1178, 1998
Direct detection of 1,1-diphenylgermene in solution and absolute rate constants for germene trapping reactions
Direct irradiation of 1,1-diphenylgermetane in hexane solution affords 1,1,3,3-tetraphenyl-1-3-digermetane in high chemical yield. Photolysis in the presence of aliphatic alcohols leads instead to the formation of the corresponding alkoxymethyldiphenylgermane. These results are consistent with the formation of 1,1-diphenylgermene as a primary photochemical product from photolysis of the germetane. Nanosecond laser flash photolysis of the compound in hexane, acetonitrile, or tetrahydrofuran gives rise to the formation of a transient, assignable to the germene on the basis of its second-order decay kinetics, UV spectrum (lambda(max) = 325 nm), and the fact that it is quenched by addition of alcohols and acetic acid. Absolute rate constants for reaction of 1.1-diphenylgermene with methanol, ethanol, 2-propanol, tert-butyl alcohol, acetic acid, the O-deuterated isotopomers, and acetone were determined in the three solvents, using the germetane as the precursor. The kinetics and mechanisms of these germene trapping reactions are discussed and compared to those of silenes.