Disparate product distributions observed in Mo((3-x))W(x)O(y) (-) (x=0-3; y=3-9) reactions with D(2)O and CO(2). 2010

David W Rothgeb, and Ekram Hossain, and Jennifer E Mann, and Caroline Chick Jarrold
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.

Results of gas phase reactivity studies on group six transition metal suboxide clusters, Mo(3)O(y) (-), Mo(2)WO(y) (-), MoW(2)O(y) (-), and W(3)O(y) (-) (Mo((3-x))W(x)O(y) (-), x=0-3; y=ca. 3-9) with both D(2)O and CO(2) are reported. Sequential oxidation for the more reduced species, Mo((3-x))W(x)O(y) (-)+D(2)O/CO(2)-->Mo((3-x))W(x)O(y+1) (-)+D(2)/CO, and dissociative addition for certain species, Mo((3-x))W(x)O(y) (-)+D(2)O/CO(2)-->Mo((3-x))W(x)O(y+1)D(2) (-)/Mo((3-x))W(x)O(y+1)CO(-), is evident in the product distributions observed in mass spectrometric measurements. Reactions with D(2)O proceed at a rate that is on the order of 10(2) higher than for CO(2). The pattern of reaction products reveals composition-dependent chemical properties of these group six unary and binary clusters. At the core of this variation is the difference in Mo-O and W-O bond energies, the latter of which is significantly higher. This results in a larger thermodynamic drive to higher oxidation states in clusters with more tungsten atoms. However, addition products for more oxidized W-rich clusters are not observed, while they are observed for the more Mo-rich clusters. This is attributed to the following: In the higher oxides (e.g., y=8), addition reactions require distortion of local metal-oxygen bonding, and will necessarily have higher activation barriers for W-O bonds, since the vibrational potentials will be narrower. The binary (x=1,2) clusters generally show sequential oxidation to higher values of y. This again is attributed to higher W-O bond energy, the result being that stable binary structures have W atoms in higher oxidation states, and Mo centers both in more reduced states and sterically unhindered. The reduced Mo center provides a locus of higher reactivity. An unusual result that is not readily explained is the chemically inert behavior of Mo(3)O(6) (-).

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