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Kinetic studies on the first dihydrogen aquacomplex, [Ru(H2)(H2O)5]2+: Formation under H2 pressure and catalytic H/D isotope exchange in water

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Title: Kinetic studies on the first dihydrogen aquacomplex, [Ru(H2)(H2O)5]2+: Formation under H2 pressure and catalytic H/D isotope exchange in water
Authors: Grundler, Pascal V.1, Yazyev, Oleg V.1, Aebischer, Nicolas1, Helm, Lothar1, Laurenczy, Gábor1, Merbach, André E. andre.merbach@epfl.ch
Source: Inorganica Chimica Acta. Apr2006, Vol. 359 Issue 6, p1795-1806. 12p.
Subjects: Nonmetals, Spectrum analysis, Surface chemistry, Catalysis
Abstract: Abstract: The ruthenium(II) hexaaqua complex [Ru(H2O)6]2+ reacts with dihydrogen under pressure to give the η2-dihydrogen ruthenium(II) pentaaqua complex [Ru(H2)(H2O)5]2+.The complex was characterized by 1H, 2H and 17O NMR: δ H =−7.65ppm, J HD =31.2Hz, δ O =−80.4 ppm (trans to H2) and δ O =−177.4ppm (cis to H2).The H–H distance in coordinated dihydrogen was estimated to 0.889Å from J HD, which is close to the value obtained from DFT calculations (0.940Å).Kinetic studies were performed by 1H and 2H NMR as well as by UV–Vis spectroscopy, yielding the complex formation rate and equilibrium constants: k f =(1.7±0.2)×10−3 kgmol−1 s−1 and K eq =4.0±0.5molkg−1.The complex formation rate with dihydrogen is close to values reported for other ligands and thus it is assumed that the reaction with dihydrogen follows the same mechanisn (I d).In deuterated water, one can observe that [Ru(H2)(H2O)5]2+ catalyses the hydrogen exchange between the solvent and the dissolved dihydrogen.A hydride is proposed as the intermediate for this exchange.Using isotope labeling, the rate constant for the hydrogen exchange on the η2-dihydrogen ligand was determined as k 1 =(0.24±0.04)×10−3 s−1.The upper and lower limits of the pK a of the coordinated dihydrogen ligand have been estimated:3
Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Kinetic studies on the first dihydrogen aquacomplex, [Ru(H<subscript>2</subscript>)(H<subscript>2</subscript>O)<subscript>5</subscript>]<superscript>2+</superscript>: Formation under H<subscript>2</subscript> pressure and catalytic H/D isotope exchange in water
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  Data: <searchLink fieldCode="AR" term="%22Grundler%2C+Pascal+V%2E%22">Grundler, Pascal V.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Yazyev%2C+Oleg+V%2E%22">Yazyev, Oleg V.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Aebischer%2C+Nicolas%22">Aebischer, Nicolas</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Helm%2C+Lothar%22">Helm, Lothar</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Laurenczy%2C+Gábor%22">Laurenczy, Gábor</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Merbach%2C+André+E%2E%22">Merbach, André E.</searchLink><i> andre.merbach@epfl.ch</i>
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  Data: <searchLink fieldCode="JN" term="%22Inorganica+Chimica+Acta%22">Inorganica Chimica Acta</searchLink>. Apr2006, Vol. 359 Issue 6, p1795-1806. 12p.
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  Data: <searchLink fieldCode="DE" term="%22Nonmetals%22">Nonmetals</searchLink><br /><searchLink fieldCode="DE" term="%22Spectrum+analysis%22">Spectrum analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Surface+chemistry%22">Surface chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink>
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  Label: Abstract
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  Data: Abstract: The ruthenium(II) hexaaqua complex [Ru(H2O)6]2+ reacts with dihydrogen under pressure to give the η2-dihydrogen ruthenium(II) pentaaqua complex [Ru(H2)(H2O)5]2+.The complex was characterized by 1H, 2H and 17O NMR: δ H =−7.65ppm, J HD =31.2Hz, δ O =−80.4 ppm (trans to H2) and δ O =−177.4ppm (cis to H2).The H–H distance in coordinated dihydrogen was estimated to 0.889Å from J HD, which is close to the value obtained from DFT calculations (0.940Å).Kinetic studies were performed by 1H and 2H NMR as well as by UV–Vis spectroscopy, yielding the complex formation rate and equilibrium constants: k f =(1.7±0.2)×10−3 kgmol−1 s−1 and K eq =4.0±0.5molkg−1.The complex formation rate with dihydrogen is close to values reported for other ligands and thus it is assumed that the reaction with dihydrogen follows the same mechanisn (I d).In deuterated water, one can observe that [Ru(H2)(H2O)5]2+ catalyses the hydrogen exchange between the solvent and the dissolved dihydrogen.A hydride is proposed as the intermediate for this exchange.Using isotope labeling, the rate constant for the hydrogen exchange on the η2-dihydrogen ligand was determined as k 1 =(0.24±0.04)×10−3 s−1.The upper and lower limits of the pK a of the coordinated dihydrogen ligand have been estimated:3<pK a <14. [Copyright &y& Elsevier]
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  Data: <i>Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1016/j.ica.2005.06.056
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        Text: English
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      – SubjectFull: Spectrum analysis
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      – SubjectFull: Surface chemistry
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      – SubjectFull: Catalysis
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      – TitleFull: Kinetic studies on the first dihydrogen aquacomplex, [Ru(H2)(H2O)5]2+: Formation under H2 pressure and catalytic H/D isotope exchange in water
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              Text: Apr2006
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