Gas-phase reactions of anionic and cationic rhodium clusters with azidoacetonitrile are studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry under near-thermal conditions. All anionic and large cationic clusters react by adding [C2,N2] in consecutive steps, either by forming interstitial carbides and nitrides or by adding two CN groups to the cluster surface. Small cationic clusters behave differently, with the unimolecular

Cold metal group 5 (V, Nb, Ta) and group 9 (Co, Rh, Ir) cationic as well as anionic clusters with up to about 30 atoms were produced by laser vaporization in supersonic expansion, and their reactivity with carbon monoxide was investigated in an FT-ICR mass spectrometer under conditions of bimolecular collisions. Anionic and cationic clusters of the later, group 9 transition metal elements, as well as cations of group 5 exhibit very similar behavior

Our studies indicate that reactivity studies of organic molecules in nanodroplets that contain hydrated electrons can yield information that is not available by pulsed radiolysis studies of bulk solutions. In the cluster study, the product compositions can be clearly identified by mass spectrometry. In the present case, it was shown that the hydrated electron induces the transfer of an H atom from water to acetonitrile. The formation of a solvent-stabilized

Absolute bimolecular rate constants for radiative stabilization of CO on gold cluster anions are measured by Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry, employing a sequence of reaction gas pulses to acquire sufficient product intensities of these exceedingly inefficient reactions. While some of the observed reactivity patterns seem to be in agreement with the jellium model if CO is viewed as a two electron donor, it cannot

Nanodroplets consisting of a central ion surrounded by a solvation shell of water molecules provide an interesting medium for studies of aqueous transition-metal chemistry in the unusual oxidation state (I). While VI undergoes efficient, solvent shell dependent redox reactions to VII and VIII, the absence of any similar reactivity in aqueous Cr(I), Mn(I), Fe(I), Co(I), Ni(I), and Cu(I) clusters is explained by a rapid precipitation of the corresponding

The reactions of hydrated aluminum ions Al(H2O)n+, 20

Hydrated vanadium cations V+(H2O)n, n=5–30, are stored in the collision-free environment of an FT-ICR mass spectrometer and their reactions due to absorption of black body radiation are studied. Besides the loss of water ligands, the clusters show two different intracluster redox reactions, whose branching ratios are strongly size-dependent. Oxidation to the +II state results in V(OH)+(H2O)n ions, and a concurrent release of atomic hydrogen. Alternatively

Metal ions in unusual oxidation states can be introduced into water clusters using a standard laser vaporization source. Such nanosolutions of a single ion in typically 50 water molecules are comparable to a 1 M bulk solution, and their chemistry can be studied in the ion trap of a Fourier transform ion cyclotron resonance mass spectrometer. We find that a strong acid like hydrogen chloride oxidizes the early transition metal vanadium to the more