A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III) Acetylacetonate

Barin E. U., Masjedi M., ÖZKAR S.

MATERIALS, vol.8, no.6, pp.3155-3167, 2015 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 8 Issue: 6
  • Publication Date: 2015
  • Doi Number: 10.3390/ma8063155
  • Journal Name: MATERIALS
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.3155-3167
  • Keywords: ruthenium, acetylacetonate, hydrogen generation, dimethylamine borane, dehydrogenation, homogeneous catalysis, METAL-ORGANIC FRAMEWORK, AMINE-BORANE, SODIUM-BOROHYDRIDE, REUSABLE NANOCATALYST, HYDROGEN GENERATION, CRYSTAL-STRUCTURE, TRANSITION-METAL, COMPLEXES, ADDUCTS, HYDROLYSIS
  • Middle East Technical University Affiliated: Yes


The catalytic activity of ruthenium(III) acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II) species is formed in situ from the reduction of ruthenium(III) and characterized using UV-Visible, Fourier transform infrared (FTIR), H-1 NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II) species is mer-[Ru(N2Me4)(3)(acac)H]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac)(3) were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy E-a = 85 +/- 2 kJmol(-1), the enthalpy of activation H-# = 82 +/- 2 kJmol(-1) and the entropy of activation; S-# = -85 +/- 5 Jmol(-1)K(-1). The ruthenium(II) catalyst formed from the reduction of ruthenium(III) acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 degrees C.