Assignment of nonclassical [Cu(CO)(n)](+) (n=1,2) complex ions in zeolite cages

A time-resolved FT-IR technique combined with an isotopic tracer method has been applied to study CO adsorbates on Cu+ ions in copper ion-exchanged zeolites. Three kinds of monocarbonyl species were found to adsorb strongly on Cu-zeolite samples after admission and subsequent evacuation of gas phase CO at room temperature. Their absorption bands were observed at 2146-2160, 2128-2150, and 2097-2129 cm(-1), respectively, dependent on the zeolite structures. In the presence of gaseous CO, the monocarbonyl species at 2146-2160 cm(-1) (so called nonclassical [Cu(CO)](+) complexes) could react with a CO molecule to form a dicarbonyl species [Cu(CO)(2)](+) with nu(sym) bands at 2169-2180 cm(-1). The reactivity of the nonclassical [Cu(CO)](+) complexes was dependent on the zeolite structures, ferrierite, mordenite > ZSM-5 > X-type reversible arrow offretite/erionite reversible arrow Y-type > L-type. The remaining two types of monocarbonyl species have Little been affected by gas phase CO.