Author:

Abstract:

As derived from in situ UV-visible-near-IR reflectance and IR transmission spectroscopy, Ru(NH 3 ) 63+ exchanged in the supercages of zeolites X and Y hydrolyzes in vacuo and in the presence of zeolite-sorbed water to [Ru(NH 3 ) 5 OH] 2+ and [(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ] 6+ (Ru-red). In air a mixture of Ru-red and [(NH 3 ) 5 RuORu(NH 3 ) 4 ORu(NH 3 ) 5 ] 7+ (Ru-brown) is obtained. These complexes are thermally unstable, and above 373 K the only identifiable complex is Ru(NO)(NH 3 ) 1,2 (O l OH,H 2 O) 4,3 . Oxygen suppresses the formation of the trimeric Ru complexes and interacts with Ru(NH 3 ) 63+ at 373 K or higher to form the nitrosyl complex. NO reacts at room temperature with Ru(NH 3 )6 3+ to form [Ru(NH 3 ) 5 N 2 ] 2+ , [Ru(NH 3 ) 5 NO] 3+ , and NH 4+ . There are slight differences between X and Y zeolites due to differences in basicities of the supercages, X being more basic than Y. In both cases after heating in vacuo or in NO the same nitrosyl complex is obtained as in other atmospheres. This chemistry of Ru(NH 3 ) 63+ in a zeolite matrix is the same as its aqueous solution chemistry. © 1981 American Chemical Society.