Vicinal Dinitridoruthenium‐Substituted Polyoxometalates γ‐[XW10O38{RuN}2]6− (X=Si or Ge) |
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Authors: | Claire Besson Djamaladdin G. Musaev Vanina Lahootun Rui Cao Lise‐Marie Chamoreau Richard Villanneau Françoise Villain René Thouvenot Yurii V. Geletii Craig L. Hill Anna Proust |
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Affiliation: | 1. Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Case courier 42, UPMC, Paris?06, 4 place Jussieu, 75252 Paris cedex (France), Fax: (+33)?1‐44‐27‐38‐41;2. Cherry L. Emerson Center for Computational Chemistry, Emory University, Atlanta GA 30322 (USA);3. Department of Chemistry, Emory University, Atlanta GA 30322 (USA);4. Synchrotron SOLEIL l'Orme des Merisiers, Saint‐Aubin BP 48, 91192 Gif sur Yvette (France);5. Institut Universitaire de France, 103, bd Saint‐Michel, 75005, Paris?103 (France) |
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Abstract: | Reaction of the divacant polyoxometalate K8[γ‐XW10O36] (X=Si, Ge) with two equivalents of the metal‐nitrido precursor Cs2[RuVINCl5], at room temperature in water, produces K2(Me2NH2)2H2[γ‐XW10O38{RuN}2], X=Si ( DMA ‐ 1 a ) or Ge ( DMA ‐ 1 b ). The X‐ray crystal structures of both complexes show monomeric complexes with highly unusual vicinal terminal metal‐nitrido units. The Ru?N bond lengths are 1.594(10) and 1.612(11) Å in 1 a and 1 b , respectively. EXAFS studies confirmed the key structural assignments from X‐ray crystallography. The XANES spectrum of DMA‐1 a , diamagnetism, NMR (29Si and 183W) chemical shifts, voltammetric behavior, reductive titrations with [PW12O40]4?, and computational data are all consistent with d2 RuVI centers in these complexes. The FT‐IR and Raman spectra show the expected vibrational modes of the {γ‐XW10} unit and the Ru?N stretch at 1080 cm?1, respectively. Interestingly, reduction of DMA‐1 a by 4 equivalents of [PW12O40]4? produces NH3 in nearly quantitative yield. Cyclic voltammetry versus pH and calculations provide the energetics for the possible two‐electron reduction and two‐proton addition processes in this reaction. |
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Keywords: | nitrides nitridoruthenium polyoxometalates ruthenium |
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