Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

Anitha S. Gowda; Sean Parkin; Folami T. Ladipo

doi:10.1002/aoc.2819

Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

Anitha S. Gowda, Sean Parkin, Folami T. Ladipo

Research output: Contribution to journal › Article › peer-review

66 Scopus citations

Abstract

The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl ₂bpy) ₂(OH ₂) ₂](Z) ₂ (1, Z = CF ₃SO ₃; 2, Z = (3,5-(CF ₃) ₂C ₆H ₃) ₄B, i.e. BArF) and cis-[Ru(4,4′-Cl ₂bpy) ₂(OH ₂) ₂](Z) ₂ (3, Z = CF ₃SO ₃; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl ₂bpy) ₂(CH ₃CN) ₂](CF ₃SO ₃) ₂ (3′) and dimeric cis-[(Ru(4,4′-Cl ₂bpy) ₂Cl) ₂](BArF) ₂ (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl ₂bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru ²⁺ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl ₂bpy) ₂(OH ₂) ₂](BArF) ₂ (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl ₂bpy) ₂(OH ₂) ₂](CF ₃SO ₃) ₂ (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds.

Original language	English
Pages (from-to)	86-93
Number of pages	8
Journal	Applied Organometallic Chemistry
Volume	26
Issue number	2
DOIs	https://doi.org/10.1002/aoc.2819
State	Published - Feb 2012

Keywords

carbon-oxygen bond hydrogenolysis
catalytic hydrogenation
furfuryl alcohol
ruthenium bis(diimine) complexes
tetrahydrofurfuryl alcohol

ASJC Scopus subject areas

General Chemistry
Inorganic Chemistry

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10.1002/aoc.2819

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@article{ea103fb16b0c4f01b462104270e04a51,

title = "Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes",

abstract = "The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](Z) 2 (1, Z = CF 3SO 3; 2, Z = (3,5-(CF 3) 2C 6H 3) 4B, i.e. BArF) and cis-[Ru(4,4′-Cl 2bpy) 2(OH 2) 2](Z) 2 (3, Z = CF 3SO 3; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl 2bpy) 2(CH 3CN) 2](CF 3SO 3) 2 (3′) and dimeric cis-[(Ru(4,4′-Cl 2bpy) 2Cl) 2](BArF) 2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl 2bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru 2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](BArF) 2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](CF 3SO 3) 2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds.",

keywords = "carbon-oxygen bond hydrogenolysis, catalytic hydrogenation, furfuryl alcohol, ruthenium bis(diimine) complexes, tetrahydrofurfuryl alcohol",

author = "Gowda, {Anitha S.} and Sean Parkin and Ladipo, {Folami T.}",

year = "2012",

month = feb,

doi = "10.1002/aoc.2819",

language = "English",

volume = "26",

pages = "86--93",

number = "2",

}

TY - JOUR

T1 - Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

AU - Gowda, Anitha S.

AU - Parkin, Sean

AU - Ladipo, Folami T.

PY - 2012/2

Y1 - 2012/2

N2 - The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](Z) 2 (1, Z = CF 3SO 3; 2, Z = (3,5-(CF 3) 2C 6H 3) 4B, i.e. BArF) and cis-[Ru(4,4′-Cl 2bpy) 2(OH 2) 2](Z) 2 (3, Z = CF 3SO 3; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl 2bpy) 2(CH 3CN) 2](CF 3SO 3) 2 (3′) and dimeric cis-[(Ru(4,4′-Cl 2bpy) 2Cl) 2](BArF) 2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl 2bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru 2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](BArF) 2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](CF 3SO 3) 2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds.

AB - The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](Z) 2 (1, Z = CF 3SO 3; 2, Z = (3,5-(CF 3) 2C 6H 3) 4B, i.e. BArF) and cis-[Ru(4,4′-Cl 2bpy) 2(OH 2) 2](Z) 2 (3, Z = CF 3SO 3; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl 2bpy) 2(CH 3CN) 2](CF 3SO 3) 2 (3′) and dimeric cis-[(Ru(4,4′-Cl 2bpy) 2Cl) 2](BArF) 2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl 2bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru 2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](BArF) 2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2](CF 3SO 3) 2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds.

KW - carbon-oxygen bond hydrogenolysis

KW - catalytic hydrogenation

KW - furfuryl alcohol

KW - ruthenium bis(diimine) complexes

KW - tetrahydrofurfuryl alcohol

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U2 - 10.1002/aoc.2819

DO - 10.1002/aoc.2819

M3 - Article

AN - SCOPUS:84856399462

SN - 0268-2605

VL - 26

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JO - Applied Organometallic Chemistry

JF - Applied Organometallic Chemistry

IS - 2

ER -

Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

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