Platinum complexes with a methoxy-amino phosphine or a nitrogen-containing bis(phosphine) ligand. Synthesis, characterization and application to hydrogenation of trans -cinnamaldehyde

Kostas, Ioannis D.; Αντωνοπούλου, Γεωργία; Potamitis, Constantinos; Raptopoulou, Catherine P.; Psycharis, Vassilis

doi:10.1016/j.jorganchem.2016.11.036

Cited by 15 publications

(8 citation statements)

References 73 publications

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“…One of the most chemically ambitious goals of this project was to test whether any of our CSMs could catalyze the selective hydrogenation of cinnamaldehyde to either the unsaturated alcohol (cinnamyl alcohol) or the saturated aldehyde (hydrocinnamaldehyde), both of which are popular pharmaceutical intermediates and fragrance ingredients . Cinnamaldehyde is often used as a model α,β-unsaturated aldehyde upon which the CC and CO selectivity of a catalyst can be tested: while reduction to the saturated aldehyde is quite simple, the selective heterogeneous hydrogenation to the unsaturated alcohol is intrinsically disfavored both kinetically and thermodynamically …”

Section: Resultsmentioning

confidence: 99%

“…These trends can be rationalized by consideration of the interactions of the atomic orbitals of each metal with olefinic and carbonylic bonds. The mode of adsorption of an α,β-unsaturated aldehyde onto a metal surface determines which group will undergo hydrogenation and is thought to be controlled by the magnitude of the four-electron repulsions between the filled d-orbitals of the metal atoms and the electron-rich CC bonds of the substrate . These four-electron repulsions are minimized by metals with contracted d-orbitals; hence, such metals favor CC over CO reduction .…”

Section: Resultsmentioning

confidence: 99%

“…71 Cinnamaldehyde is often used as a model α,β-unsaturated aldehyde upon which the CC and CO selectivity of a catalyst can be tested: while reduction to the saturated aldehyde is quite simple, the selective heterogeneous hydrogenation to the unsaturated alcohol is intrinsically disfavored both kinetically and thermodynamically. 72 Figure 11 shows the results of the cinnamaldehyde reduction tests over the aluminous CSMs. The activity of both the Ni− Al 2 O 3 and Ru−Al 2 O 3 CSMs was similar, but the low activity of the ruthenium is somewhat surprising, especially considering its excellent performance in the tests with linalool and citronellal.…”

Section: Resultsmentioning

confidence: 99%

“…The mode of adsorption of an α,βunsaturated aldehyde onto a metal surface determines which group will undergo hydrogenation 73 and is thought to be controlled by the magnitude of the four-electron repulsions between the filled d-orbitals of the metal atoms and the electron-rich CC bonds of the substrate. 72 These fourelectron repulsions are minimized by metals with contracted dorbitals; hence, such metals favor CC over CO reduction. 72 As the d-band width increases across the series Ni < Pd < Ru < Pt, 74 it is expected that nickel and palladium are far more selective for CC reduction, which has been supported by numerous DFT, NEXAFS, and experimental studies 75 and accounts for the behavior of the Pd−Al 2 O 3 CSMs.…”

Section: Resultsmentioning

confidence: 99%

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Continuous Flow Hydrogenation of Flavorings and Fragrances Using 3D-Printed Catalytic Static Mixers

Kundra

Grall

et al. 2021

Ind. Eng. Chem. Res.

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A new type of additively manufactured catalytic static mixer, coated with alumina-supported metal catalysts, has been used for the hydrogenation of various model compounds commonly employed in the flavoring and fragrance industries. These heterogeneous catalytic reactions were performed inside an intensified tubular flow reactor housing several catalytic static mixers. In addition to electroplated and cold-sprayed catalyst coatings, which were presented by our group in earlier work, we herein demonstrate a series of alumina-supported metal catalysts for the first time, namely Pd, Pt, Ru, and Ni, supported on alumina and deposited on stainless-steel static mixers. The continuous flow hydrogenation of (−)-isopulegol at 24 bar and 130 °C produced the high value product (−)-menthol at full conversion with a 98.8% purity and a space-time yield of 2.66 kg L −1 h −1 .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Continuous Flow Hydrogenation of Flavorings and Fragrances Using 3D-Printed Catalytic Static Mixers

Kundra

Grall

et al. 2021

Ind. Eng. Chem. Res.

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“…We note that the -CH 3 and =CH 2 groups are often disordered in the solid state, since they occupy similar volumes within the unit cell. satellites with values similar to 5 [25,26]. The FT−IR spectrum shows two ν PtCl vibrations (316 and 291 cm −1 ) consistent with cis-chelation and an ν NH vibration at 3358 cm −1 .…”

Section: < Insert Scheme 2 and Scheme 2 Caption Here >mentioning

confidence: 66%

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

Cao

Elsegood

Lastra-Calvo

et al. 2017

Journal of Organometallic Chemistry

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Controlled stepwise reaction of a geminal substituted alkene or primary amine group afforded a small library of new functionalised tertiary and ditertiary phosphines. Accordingly, Mannich based condensation of the commercially available disubstituted arene C 6 H 4 (NH 2){2-C(Me)=CH 2 } with HOCH 2 PR 2 (R 2 = Cg: 1,3,5,7-tetramethyl-2,4,8-trioxa-6phosphaadamantyl; Ph 2) afforded the (aminomethyl)phosphines C 6 H 4 (NHCH 2 PCg){2-C(Me)=CH 2 } L 1 and C 6 H 4 (NHCH 2 PPh 2){2-C(Me)=CH 2 } L 2 in approx. 60% yield. In addition to the formation of L 2 , the diphosphine L 3 was also identified and independently synthesised upon reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with two equiv. of HOCH 2 PPh 2 in CH 3 OH under reflux. Alternatively, reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with H-PR 2 (R 2 = Cg or Ph 2) in the presence of AIBN [2,2`-azobis(2-methylpropionitrile)] as free radical initiator, afforded the primary amine functionalised phosphines C 6 H 4 (NH 2){2-CH(Me)CH 2 PCg} L 4 and C 6 H 4 (NH 2){2-CH(Me)CH 2 PPh 2 } L 5 in 85% and 66% isolated yields respectively. In both cases only the anti-Markovnikov addition products were observed. Subsequent reaction of L 5 with HOCH 2 PR 2 (R 2 = Ph 2) afforded the unsymmetrical ditertiary phosphine C 6 H 4 (NHCH 2 PPh 2){2-CH(Me)CH 2 PPh 2 } L 6. Some preliminary coordination studies towards [RuCl(µ-Cl)(η 6-C 10 Η 14)] 2, [AuCl(tht)] (tht = tetrahydrothiophene) and [MCl 2 (η 4-cod)] (M = Pd, Pt; cod = cycloocta-1,5-diene) demonstrate these new ligands behave as classic P-donors leaving the pendant amino or alkenyl groups non-coordinating. All compounds have been characterised by multinuclear NMR, FT−IR, mass spectrometry and microanalysis. Single crystal X-ray studies have been performed on L 3 , L 5 , L 6 , 1, 3b•0.5CH 2 Cl 2 , 4a•1.5CH 2 Cl 2 , 5 and 6•0.5CDCl 3 •0.5C 4 H 10 O

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A Sustainable Approach to Selective Hydrogenation of Unsaturated Esters and Aldehydes with Ruthenium Catalysts

et al. 2023

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The reduction of esters and aldehydes to alcohols is an important reaction in the chemical industry to produce a wide range of bulk and fine chemicals. Herein, the unexpected behavior of three state-of-the-art, commercially available Rucatalysts for the hydrogenation of these feedstocks is reported. For ester and aldehydes containing a C=C bond, it was possible to carry out the selective hydrogenation of the ester or aldehyde functionality while keeping the C=C double-bond essentially untouched. Furthermore, it is demonstrated that these substrates can be reduced under very mild reaction conditions (as low as 40 °C and 5 bar of H 2 ) and that anisole, a solvent with a high sustainability rank, is suitable for these catalytic hydrogenations.

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Platinum complexes with a methoxy-amino phosphine or a nitrogen-containing bis(phosphine) ligand. Synthesis, characterization and application to hydrogenation of trans -cinnamaldehyde

Cited by 15 publications

References 73 publications

Continuous Flow Hydrogenation of Flavorings and Fragrances Using 3D-Printed Catalytic Static Mixers

Continuous Flow Hydrogenation of Flavorings and Fragrances Using 3D-Printed Catalytic Static Mixers

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

A Sustainable Approach to Selective Hydrogenation of Unsaturated Esters and Aldehydes with Ruthenium Catalysts

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