Synthesis and characterisation of a range of Fe, Co, Ru and Rh triphos complexes and investigations into the catalytic hydrogenation of levulinic acid
File(s)
Accepted version
Author(s)
Type
Journal Article
Abstract
The coordination chemistry of the N-triphos ligand (NP3Ph, 1b) has been investigated with range of Fe, Co and Rh precursors and found to form either tridentate or bidentate complexes. Reaction of NP3Ph with [Rh(COD)(CH3CN)2]BF4 resulted in the formation of the tridentate complex [Rh(COD)(κ3 NP3Ph)]BF4 (3) in the solid state, however, in solution a bidentate complex predominates in more polar solvents. Reaction of NP3Ph with Fe carbonyl precursors revealed the formation of the bidentate complexes [Fe(CO)3(κ2-NP3Ph)Fe(CO)4] (4) and [Fe(CO)3(κ2-NP3Ph)] (5), while reaction with FeBr2 resulted in the paramagnetic bidentate complex [Fe(Br)2(κ2-NP3Ph)] (6). Reaction of NP3Ph with CoCl2 gave a dimeric Co species [(κ2-NP3Ph)CoCl(κ1,κ2-NP3Ph)CoCl3] (7), while Zn powder reduction of NP3Ph Co halides resulted in the formation of the tridentate complexes of the type: [Co(X)(k3-NP3Ph)]. The related triphos Ru complex, [Ru(CO3)(CO)(κ3-CP3Ph)] (2), has also been isolated and characterised. Preliminary catalytic hydrogenation of levulinic acid (LA) was conducted with 2 and 3. The Ru complex was found to be catalytically active, giving high conversions of LA to form gamma valerolactone (GVL) and 1,4-pentandiol (1,4-PDO), while 3 was found to be catalytically inactive. In situ catalytic testing with 1b and Fe(BF4)2.6H2O resulted in low conversions of LA while a combination of 1b and Co(BF4)2.6H2O gave higher conversions 75% yields of GVL.
Date Issued
2021-03-01
Date Acceptance
2020-12-04
Citation
Journal of Organometallic Chemistry, 2021, 935, pp.1-12
ISSN
0022-328X
Publisher
Elsevier BV
Start Page
1
End Page
12
Journal / Book Title
Journal of Organometallic Chemistry
Volume
935
Copyright Statement
© 2020 Elsevier Ltd. All rights reserved. This manuscript is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International Licence http://creativecommons.org/licenses/by-nc-nd/4.0/
Identifier
https://www.sciencedirect.com/science/article/pii/S0022328X20305532?via%3Dihub
Subjects
Organic Chemistry
0302 Inorganic Chemistry
0305 Organic Chemistry
0399 Other Chemical Sciences
Publication Status
Published
Article Number
121650
Date Publish Online
2020-12-08