Show/Hide Menu
Hide/Show Apps
anonymousUser
Logout
Türkçe
Türkçe
Search
Search
Login
Login
OpenMETU
OpenMETU
About
About
Open Science Policy
Open Science Policy
Communities & Collections
Communities & Collections
Help
Help
Frequently Asked Questions
Frequently Asked Questions
Videos
Videos
Thesis submission
Thesis submission
Publication submission with DOI
Publication submission with DOI
Publication submission
Publication submission
Contact us
Contact us
Highly active and long lived homogeneous catalyst for the dehydrogenation of dimethylamine borane starting with ruthenium(III) acetylacetonate and oleylamine precatalyst
Date
2016-01-01
Author
DUMAN, SİBEL
Masjedi, Mehdi
Özkar, Saim
Metadata
Show full item record
This work is licensed under a
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
.
Item Usage Stats
5
views
0
downloads
Cite This
Herein, we report the results of our study on the homogeneous catalytic dehydrogenation of dimethylamine borane in the presence of Ru(acac)(3) and oleylamine (OAm) in toluene solution. The precatalyst system comprising Ru(acac)(3) and 3 equivalent OAm shows the high catalytic activity in hydrogen generation from dimethylamine borane solution. Monitoring the hydrogen evolution shows the presence of an induction period during which the homogeneous catalyst is formed, and then the hydrogen evolution continues almost linearly until the complete dehydrogenation of dimethylamine borane. UV-vis spectroscopic observation implies on the formation of a ruthenium(II)species. Using UV-vis, FTIR, Mass, H-1 and C-13 NMR spectroscopies we could identify the presence of trans-[Ru(acac)(2)(OAm)(2)] in the solid residue obtained after the catalytic reaction. This complex might be a stable form of the active catalyst as it shows similar catalytic activity in dehydrogenation of dimethylamine borane as before. The precatalyst system comprising Ru(acac)(3) and 3 equivalent OAm provides 15,000 turnovers over 8 days with a constant turnover frequency of TOP = 77.8 h(-1) in hydrogen generation from the dehydrogenation of dimethylamine borane in toluene solution at 60.0 +/- 0.1 degrees C. Adding 3 equivalent OAm per Ru into the precatalyst solution increases the catalytic activity by a factor of similar to 5 and the lifetime of the catalyst by a factor of >9 compared to the ones obtained by using sole Ru(acac)(3). Kinetics of catalytic dehydrogenation of dimethylamine borane starting with Ru(acac)(3) and 3 equivalent OAm in toluene solution were studied depending on catalyst concentration, substrate concentration and temperature. The catalytic reaction was found to be first-order with respect to each of both Ru(acac)(3) and dimethylamine borane concentrations. The activation energy for the catalytic dehydrogenation is E-a = 58 +/- 2 kJ/mol. (C) 2015 Published by Elsevier B.V.
Subject Keywords
Ruthenium acetylacetonate
,
Oleylamine
,
Hydrogen generation
,
Dimethylamine borane
,
Dehydrogenation
,
Homogeneous catalysis
URI
https://hdl.handle.net/11511/43842
Journal
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
DOI
https://doi.org/10.1016/j.molcata.2015.08.006
Collections
Department of Chemistry, Article
Citation Formats
IEEE
ACM
APA
CHICAGO
MLA
BibTeX
S. DUMAN, M. Masjedi, and S. Özkar, “Highly active and long lived homogeneous catalyst for the dehydrogenation of dimethylamine borane starting with ruthenium(III) acetylacetonate and oleylamine precatalyst,”
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
, vol. 411, pp. 9–18, 2016, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/43842.