The reactions of free, size selected gold and silver cluster cations Ag-n(+) and Au-n(+) (n = 3, 5) with C6H6 as well as with a mixture of C6H6 and CO were investigated in a radio frequency ion trap under multiple collision condition. While benzene was found to react with all investigated metal clusters exhibiting size dependent adsorbate coverages, the coadsorption of C6H6 and CO was only observed on the gold clusters. Photodissociation experiments at 353 and 393 nm, respectively, provided indications for charge transfer induced fragmentation in the case of the silver cluster-benzene complexes. In particular, for Ag-5(C6H6)(2)(+) the femtosecond time resolved fragmentation dynamics could be measured. (C) 2009 Elsevier B.V. All rights reserved.