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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Main Authors: Verónica Caballero, Rafael Estevez, Diego Luna, Felipa M. Bautista, Antonio A. Romero, Laura Aguado-Deblas, Jesús Hidalgo-Carrillo, Isabel Romero
Format: Article
Language:English
Published: MDPI AG 2021-02-01
Series:Catalysts
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Online Access:https://www.mdpi.com/2073-4344/11/2/289
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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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