Hydroxyalkyl silver radicals, Ag-CH,OH + in y-irradiated Ag-NaA zeolites with adsorbed methanol have been studied by EPR spectroscopy. These adducts, for silver loadings greater than one Ag' per unit cell, are formed directly after irradiation at 77 K. For lower A g + content they appear on annealing above 140 K. It is postulated that the A g + location in the zeolite lattice plays a crucial role in this process, and t w o different mechanisms of Ag-CH,OH+ formation are discussed depending on Ag+ location inside or outside a P-cage.Silver atoms and silver clusters formed in various frozen solutions by ionizing radiation have been extensively studied by EPR spectroscopy. 1-7 Recently radiation-induced silver agglomeration in zeolites has attracted special interest.8-' Much less is known about the organosilver radicals formed during radiation processes. EPR doublets with relatively low silver isotropic hyperfine couplings were first observed in yirradiated frozen methanol solutions: A,,,(Ag) ca. 13.0 mT. A similar doublet was later reported for glassy ethanol samples. l 8 Based on detailed analysis of EPR doublets for CD,OD and 3CH30H samples, Symons" assigned them to covalent organosilver radicals, A g C H 2 0 H + and AgCHCH,OH + having a single electron 0 ' bond between silver and carbon. The same author has proposed that they are formed by Ceaction between. Ag + cations and matrix-derived radicals, C H 2 0 H or CH,CHOH. Besides alcohol glasses Ag doublets with highly reduced A values were only reported for yirradiated frozen solutions of CD,CN + D 2 0 mixtures, A,,,(Ag) = 17.5 mT4 and in glassy dimethylformamide, A,,,(Ag) = 10.0 mT.6The same type of organosilver radicals have also been generated by matrix isolation techniques but only in 1989,85,3963.
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