Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports
In this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [Ru<sup>II</sup>Cl (bpea){(S)(-)(BINAP)}](BF<sub>4</sub>), <b>1,</b> and [Ru<sup>II</sup>Cl(bpea)(DPPE)](BF<sub>4</sub>), <b>2</b>, where BINAP = 2,...
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2021-02-01
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author | Verónica Caballero Rafael Estevez Diego Luna Felipa M. Bautista Antonio A. Romero Laura Aguado-Deblas Jesús Hidalgo-Carrillo Isabel Romero |
author_facet | Verónica Caballero Rafael Estevez Diego Luna Felipa M. Bautista Antonio A. Romero Laura Aguado-Deblas Jesús Hidalgo-Carrillo Isabel Romero |
author_sort | Verónica Caballero |
collection | DOAJ |
description | In this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [Ru<sup>II</sup>Cl (bpea){(S)(-)(BINAP)}](BF<sub>4</sub>), <b>1,</b> and [Ru<sup>II</sup>Cl(bpea)(DPPE)](BF<sub>4</sub>), <b>2</b>, where BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO<sub>4</sub>-Sepiolite@<b>1</b> and AlPO<sub>4</sub>-Sepiolite@<b>2</b>) by using a N-tridentate ligand N,N-bis-(2-pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO<sub>4</sub>-Sepiolite (20/80) inorganic support. This AlPO<sub>4</sub>-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) than the amorphous AlPO<sub>4</sub> (0.89%). Both heterogenized complexes have been assessed as catalysts in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds using methanol as solvent, attaining good catalytic activity and high enantioselectivity (99%). The highest Turn Over Number (TON) value (748.6) was obtained over the [Ru<sup>II</sup> Cl (bpea)(DPPE)](BF<sub>4</sub>) <b>2</b> catalyst, although the [Ru<sup>II</sup>Cl(bpea){(S)(-)(BINAP)}](BF<sub>4</sub>) <b>1</b> exhibits better reusability. In fact, the [Ru<sup>II</sup>Cl(bpea){(S)(-)(BINAP)}](BF<sub>4</sub>) immobilized on AlPO<sub>4</sub>-Sepiolite maintained the activity throughout 14 successive runs. Furthermore, some findings on hydrogenation mechanisms of the α,β-unsaturated carbonyl compounds over Ru catalysts have been also obtained. |
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spelling | doaj.art-f4e33b7dfb874c0ebb56ec2096a6ee012023-12-11T18:00:39ZengMDPI AGCatalysts2073-43442021-02-0111228910.3390/catal11020289Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite SupportsVerónica Caballero0Rafael Estevez1Diego Luna2Felipa M. Bautista3Antonio A. Romero4Laura Aguado-Deblas5Jesús Hidalgo-Carrillo6Isabel Romero7Departamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, SpainDepartament de Química and Serveis Tècnics de Recerca, Universitat de Girona, C/M. Aurèlia Campmany, 69, E-17003 Girona, SpainIn this work, the covalent immobilization of two ruthenium(II) complexes, i.e., [Ru<sup>II</sup>Cl (bpea){(S)(-)(BINAP)}](BF<sub>4</sub>), <b>1,</b> and [Ru<sup>II</sup>Cl(bpea)(DPPE)](BF<sub>4</sub>), <b>2</b>, where BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO<sub>4</sub>-Sepiolite@<b>1</b> and AlPO<sub>4</sub>-Sepiolite@<b>2</b>) by using a N-tridentate ligand N,N-bis-(2-pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO<sub>4</sub>-Sepiolite (20/80) inorganic support. This AlPO<sub>4</sub>-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) than the amorphous AlPO<sub>4</sub> (0.89%). Both heterogenized complexes have been assessed as catalysts in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds using methanol as solvent, attaining good catalytic activity and high enantioselectivity (99%). The highest Turn Over Number (TON) value (748.6) was obtained over the [Ru<sup>II</sup> Cl (bpea)(DPPE)](BF<sub>4</sub>) <b>2</b> catalyst, although the [Ru<sup>II</sup>Cl(bpea){(S)(-)(BINAP)}](BF<sub>4</sub>) <b>1</b> exhibits better reusability. In fact, the [Ru<sup>II</sup>Cl(bpea){(S)(-)(BINAP)}](BF<sub>4</sub>) immobilized on AlPO<sub>4</sub>-Sepiolite maintained the activity throughout 14 successive runs. Furthermore, some findings on hydrogenation mechanisms of the α,β-unsaturated carbonyl compounds over Ru catalysts have been also obtained.https://www.mdpi.com/2073-4344/11/2/289ruthenium complexescovalent heterogenizationDPPE ligandBINAP ligandbpea ligandenantioselective hydrogenation |
spellingShingle | Verónica Caballero Rafael Estevez Diego Luna Felipa M. Bautista Antonio A. Romero Laura Aguado-Deblas Jesús Hidalgo-Carrillo Isabel Romero Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports Catalysts ruthenium complexes covalent heterogenization DPPE ligand BINAP ligand bpea ligand enantioselective hydrogenation |
title | Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports |
title_full | Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports |
title_fullStr | Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports |
title_full_unstemmed | Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports |
title_short | Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO<sub>4</sub>-Sepiolite Supports |
title_sort | hydrogenation of α β unsaturated carbonyl compounds over covalently heterogenized ru ii diphosphine complexes on alpo sub 4 sub sepiolite supports |
topic | ruthenium complexes covalent heterogenization DPPE ligand BINAP ligand bpea ligand enantioselective hydrogenation |
url | https://www.mdpi.com/2073-4344/11/2/289 |
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