Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. Journal articles
  4. Kinetic studies on the first dihydrogen aquacomplex, [Ru(H2)(H2O)5]2+: Formation under H2 pressure and catalytic H/D isotope exchange in water
 
Loading...
Thumbnail Image
research article

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

Grundler, Pascal V.
•
Yazyev, Oleg V.  
•
Aebischer, Nicolas
Show more
2006
Inorganica Chimica Acta

The ruthenium(II) hexaaqua complex [Ru(H2O)6]2+ reacts with dihydrogen under pressure to give the h2-dihydrogen ruthenium(II) pentaaqua complex [Ru(H2)(H2O)5]2+.The complex was characterized by 1H, 2H and 17O NMR: d H = -7.65 ppm, J HD = 31.2 Hz, d O = -80.4 ppm (trans to H2) and d O = -177.4 ppm (cis to H2).The H-H distance in coordinated dihydrogen was estd. to 0.889 .ANG. from J HD, which is close to the value obtained from DFT calcns. (0.940 .ANG.). Kinetic studies were performed by 1H and 2H NMR as well as by UV-Vis spectroscopy, yielding the complex formation rate and equil. consts.: k f = (1.7 +- 0.2) * 10-3 kg mol-1 s-1 and K eq = 4.0 +- 0.5 mol kg-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+ catalyzes 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 const. for the hydrogen exchange on the h2-dihydrogen ligand was detd. 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 estd.:3 < pK a < 14.

  • Files
  • Details
  • Metrics
Loading...
Thumbnail Image
Name

inorgchimacta2006.pdf

Access type

restricted

Size

300.69 KB

Format

Adobe PDF

Checksum (MD5)

5ca978cf8f33aaf74bd6eabd8d8de7d9

Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés