Geometric isomerization and geometry controlled catalytic alcohol aminations of ruthenium hydride compounds containing bidentate pyrrolyl-imines

Yong Jie Li, Hsuan Ting Lai, Ching Han Hu, Jie Hong Chen, Chia Her Lin, Jui Hsien Huang

Research output: Contribution to journalArticle

Abstract

A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.

Original languageEnglish
Article number120957
JournalJournal of Organometallic Chemistry
Volume902
DOIs
Publication statusPublished - 2019 Dec 1

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Ruthenium Compounds
Amination
Imines
Ruthenium
Isomerization
Hydrides
imines
isomerization
ruthenium
hydrides
alcohols
Alcohols
Ligands
Carbon Monoxide
ligands
Geometry
geometry
methylidyne
Temperature
Benzyl Alcohol

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{9694eb558d5b48a9b2b3697053ec48ff,
title = "Geometric isomerization and geometry controlled catalytic alcohol aminations of ruthenium hydride compounds containing bidentate pyrrolyl-imines",
abstract = "A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.",
author = "Li, {Yong Jie} and Lai, {Hsuan Ting} and Hu, {Ching Han} and Chen, {Jie Hong} and Lin, {Chia Her} and Huang, {Jui Hsien}",
year = "2019",
month = "12",
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doi = "10.1016/j.jorganchem.2019.120957",
language = "English",
volume = "902",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",

}

Geometric isomerization and geometry controlled catalytic alcohol aminations of ruthenium hydride compounds containing bidentate pyrrolyl-imines. / Li, Yong Jie; Lai, Hsuan Ting; Hu, Ching Han; Chen, Jie Hong; Lin, Chia Her; Huang, Jui Hsien.

In: Journal of Organometallic Chemistry, Vol. 902, 120957, 01.12.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Geometric isomerization and geometry controlled catalytic alcohol aminations of ruthenium hydride compounds containing bidentate pyrrolyl-imines

AU - Li, Yong Jie

AU - Lai, Hsuan Ting

AU - Hu, Ching Han

AU - Chen, Jie Hong

AU - Lin, Chia Her

AU - Huang, Jui Hsien

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N2 - A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.

AB - A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.

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