Addition of H(2)O and D(2)O to small tungsten suboxide cluster anions W(x)O(y)(-) (x = 1-4; y < or = 3x) was studied using mass spectrometric measurements from a high-pressure fast flow reactor. Within the WO(y)(-) mass manifold, which also includes WO(4)H(-), product masses correspond to the addition of one to three H(2)O or D(2)O molecules. Within the W(2)O(y)(-) cluster series, product distributions suggest that sequential oxidation W(2)O(y)(-) + H(2)O/D(2)O --> W(2)O(y+1)(-) + H(2)/D(2) occurs for y < 5, while for W(2)O(5)(-), W(2)O(6)H(2)(-)/W(2)O(6)D(2)(-) is primarily produced. W(2)O(6)(-) does not appear reactive. For the W(3)O(y)(-) cluster series, sequential oxidation with H(2) and D(2) production occurs for y < 6, while W(3)O(6)(-) and W(3)O(7)(-) produce W(3)O(7)H(2)(-)/W(3)O(7)D(2)(-) and W(3)O(8)H(2)(-)/W(3)O(8)D(2)(-), respectively. Lower mass resolution in the W(4)O(y)(-) mass range prevents definitive product assignments, but intensity patterns suggest that sequential oxidation with H(2)/D(2) evolution occurs for y < 6, while W(4)O(y+1)H(2)(-)/W(4)O(y+1)D(2)(-) products result from addition to W(4)O(6)(-) and W(4)O(7)(-). Based on bond energy arguments, the H(2)/D(2) loss reaction is energetically favored if the new O-W(x)O(y)(-) bond energy is greater than 5.1 eV. The relative magnitude of the rate constants for sequential oxidation and H(2)O/D(2)O addition for the x = 2 series was determined. There are no discernable differences in rate constants for reactions with H(2)O or D(2)O, suggesting that the H(2) and D(2) loss from the lower-oxide/hydroxide intermediates is very fast relative to the addition of H(2)O or D(2)O.

The structures of Mo(3)O(6), Mo(2)WO(6), MoW(2)O(6), and W(3)O(6) and their associated anions were studied using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. The 3.49 eV photon energy anion PE spectra of all four species showed broad electronic bands with origins near 2.8 eV. Calculations predict that low-spin, cyclic structures are the lowest energy isomers for both the anion and neutral species. The lowest energy neutral structures for all four species are analogous, C(3v) (Mo(3)O(6) and W(3)O(6)) or C(s) (mixed clusters) symmetry structures in which all three metal atoms are in formally equivalent oxidation states, with singlet ground electronic states. The lowest energy isomers predicted for Mo(3)O(6)(-) and W(3)O(6)(-) are the same with doublet electronic states. The lowest energy structures calculated for the mixed anions are lower symmetry, with the tungsten centers in higher oxidation states than the molybdenum centers. However, C(s) symmetry structures are competitive, and appear to be the primary contributors to the observed spectra. Spectral simulations based on calculated spectroscopic parameters validate the assignments. This series of clusters is strikingly different from the Mo(2)O(4)/MoWO(4)/W(2)O(4) anion and neutral series described recently [Mayhall et al., J. Chem. Phys. 130, 124313 (2009)]. While the average oxidation state is the same for both series, the structures determined for the Mo(2)O(4)/MoWO(4)/W(2)O(4) anions and neutrals were dissimilar and lower symmetry, and high spin states were energetically favored. This difference is attributed to the large stabilizing effect of electronic delocalization in the more symmetric trimetallic cyclic structures that is not available in the bimetallic species.