Abstract
Ruthenium ions in zeolite Y form complexes with CO and O/sub 2/ which have well-resolved EPR spectra. Addition of CO at 298/sup 0/K resulted in the formation of a Ru/sup 3 +/ monocarbonyl complex or a polycarbonyl complex, depending on the partial pressure of CO. The monocarbonyl complex was characterized by g/sub perpendicular/ = 2.0600 and g/sub parallel/ to = 1.9871, whereas the polycarbonyl complex was characterized by g/sub perpendicular/ = 2.0593, g/sub 2/ = 2.471, and g/sub 3/ = 1.9970. Hyperfine coupling for /sup 13/C and the two ruthenium isotopes, /sup 99/Ru and /sup 101/Ru, indicates that the unpaired electron is primarily localized (ca. 70%) on the metal ion. Upon reaction of the monocarbonyl complex with O/sub 2/ at 298 K, the spectrum of a superoxide ion was observed. The Ru/sup 3 +/ appears to be oxidized to Ru/sup 4 +/, and the reversible nature of the spectrum indicates that CO and O/sub 2/ are simultaneously coordinated to the ruthenium. The spectrum of the complex formed with /sup 17/O/sub 2/ suggests that the oxygen nuclei are nonequivalent.
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