
Journal of Organometallic Chemistry (2021)
Update date:2022-08-11
Topics:
Omoruyi, Uwaila
Page, Samuel J.
Apps, Samantha L.
White, Andrew J.P.
Long, Nicholas J.
Miller, Philip W.
The coordination chemistry of the N-triphos ligand (NP3Ph, 1b) has been investigated with a 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(κ1,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)(κ3-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-vvvalerolactone (GVL) and 1,4-pentanediol (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 high conversions to GVL.
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