Nitric oxide binding to and/or dissociation on isolated cobalt cluster cations, Con
+
(n = 3–14), has
been investigated using a combination of infrared multiple-photon dissociation spectroscopy and
density functional theory. Rich vibrational structure in the 300 – 800 cm−1 spectral region reflects
predominantly dissociative adsorption though a minor molecularly bound isomer cannot be ruled
out. Inert messenger tagging reveals nitrogen and oxygen atoms bound in bridged and/or three
atom sites. The calculated potential energy surface associated with the reaction between NO and
Co3
+
confirms only submerged barriers to dissociation and unusual full insertion of the N atom
which binds to all three metal atoms. The second NO adsorbed also dissociates on all clusters
studied here, with the smallest cluster, [Co3N2O2]
+
-Arm, adopting an unusual planar cyclic
structure with O atoms and an N2 molecule inserted between adjacent Co atoms.
infrared photodissociation spectroscopy
,NO dissociation
,cobalt clusters
