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P FTIR spectroscopic study of CO adsorption on Co–ZSM-5: C + Evidence of formation of Co (CO)4 species C K. Hadjiivanov,*a B. Tsyntsarski,a Tz. Venkov,a D. Klissurski,a M. Daturi,b J. Sausseyb and P J.-C. Lavalleyb a Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria. E-mail: kih@svr.igic.bas.bg; Fax: +359 2 705024; Tel: +359 2 9793598 b ´ ´ Laboratoire Catalyse et Spectrochimie, CNRS-ISMRA, Universite de Caen, 6, bd Marechal Juin, 14050 Caen Cedex, France Received 21st January 2003, Accepted 25th February 2003 First published as an Advance Article on the web 5th March 2003 CO adsorption on Co–ZSM-5 results in formation of two kinds of Co2+–CO species characterized by bands at 2217 and 2207 cm1, respectively. The species are highly resistant towards evacuation at ambient temperature. When CO adsorption is performed at low temperature, new kinds of weakly electrophilic Co2+ sites are evidenced by carbonyl bands at 2197 and 2190 cm1. The bands detected at ambient temperature are negligibly reduced in intensity, suggesting initial stages of formation of geminal Co2+(CO)2 dicarbonyls (most probably absorbing at 2201 cm1). Reduction of the sample in a CO atmosphere at temperatures of 423–673 K results in creation of a fraction of Co+ cations. The latter form, with CO, stable Co+(CO)2 dicarbonyl species (bands at 2113 and 2042 cm1). Coadsorption of 12CO and 13CO allows detection of Co+(12CO)(12CO) (2097 and 2013 1