Hydrogenation of nitroaromatics to anilines catalyzed by air‐stable arene ruthenium (II)–NNN pincer complexes

Pitchaimani, Jayaraman; Gunasekaran, N.; Anthony, Savarimuthu Philip; Moon, Dohyun; Madhu, Vedichi

doi:10.1002/aoc.4689

Cited by 8 publications

(7 citation statements)

References 34 publications

(19 reference statements)

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“…UV‐Vis and 1 H NMR spectral experiments confirm that the reduction proceeds through pathway A. In this study, Ru complexes were reacted with NaBH 4 in ethanol, similar to those reported in the literature 28,76,80 . Unfortunately, the intermediate Ru‐H could not be isolated in 1 H NMR.…”

Section: Resultssupporting

confidence: 79%

“…In this study, Ru complexes were reacted with NaBH 4 in ethanol, similar to those reported in the literature. 28,76,80 Unfortunately, the intermediate Ru-H could not be isolated in 1 H NMR. However, in nitro reduction reactions, considering the literature data, 2,28,76,80 we predict that the Ru-H intermediate is formed during the catalytic reaction of the obtained ruthenium complexes.…”

Section: The Mechanistic Insightsmentioning

confidence: 99%

“…Ruthenium complexes are widely used as homogeneous catalysts in the reduction reactions of nitro compounds due to their high catalytic activity 24,26–28 . However, to the best of our knowledge, the use of Ru complexes containing RuCl 2 (PPh 3 ) 3 and RuHCl(CO)(PPh 3 ) 3 salts with N ‐acyl thiourea ligands as homogeneous catalysts for the hydrogenation of nitroarenes has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%

“…26 Ruthenium complexes are widely used as homogeneous catalysts in the reduction reactions of nitro compounds due to their high catalytic activity. 24,[26][27][28] However, to the best of our knowledge, the use of Ru complexes containing RuCl 2 (PPh 3 ) 3 and RuHCl(CO) (PPh 3 ) 3 salts with N-acyl thiourea ligands as homogeneous catalysts for the hydrogenation of nitroarenes has not yet been reported. Therefore, in this study, we performed the synthesis and characterization of paramagnetic Ru(II) and diamagnetic Ru(III) complexes with two benzoylthiourea derivative ligands.…”

Section: Introductionmentioning

confidence: 99%

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Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Uysal

Solmaz

Arslan

2023

Applied Organom Chemis

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Four ruthenium complexes {[RuCl(CO)(PPh 3 ) 2 L 1 ], [RuCl(CO)(PPh 3 ) 2 L 2 ],[RuCl 2 (PPh 3 ) 2 L 1 ] and [RuCl 2 (PPh 3 ) 2 L 2 ]} supported with N-acylthiourea-based ligands were synthesized. The compounds prepared were characterized by 1 H NMR, 13 C NMR, elemental analysis, UV-vis, and magnetic susceptibility methods. The characterization of the molecular structure of two ruthenium complexes {[RuCl(CO)(PPh 3 ) 2 L 1 ] and [RuCl 2 (PPh 3 ) 2 L 1 ]} was also performed using the single crystal X-ray diffraction method. Single crystal X-ray analyses indicates the existence of different non-covalent interactions between different parts of the molecules, which led to the formation of three-dimensional supramolecular architectures and synthons. The magnetic susceptibility and UV-vis spectra of the prepared ruthenium complexes propose that they are of low-spin states, where Ru(II) is d 6 and Ru(III) is d 5 low spin. These ruthenium compounds functioned as catalysts for the NaBH 4 -mediated reduction of various nitro compounds. The catalytic results show that the [RuCl 2 (PPh 3 ) 2 L] type complexes exhibit higher catalytic activity than the [RuCl(CO)(PPh 3 ) 2 L] type complexes, and [RuCl 2 (PPh 3 ) 2 L 1 ] has high catalytic selectivity and efficiency in a short time (>99 yield with catalyst loading 0.01 mol in 0.5 h). Furthermore, the catalytic activity of [RuCl 2 (PPh 3 ) 2 L 1 ] was investigated using nitrobenzene as a model substrate to understand the reaction pathway, and this study proved that this nitro reduction proceeds via a direct pathway, with the formation of N-hydroxylamine as the main intermediate followed by the occurrence of aniline.

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Section: Resultssupporting

confidence: 79%

Section: The Mechanistic Insightsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Uysal

Solmaz

Arslan

2023

Applied Organom Chemis

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“…It can dramatically promote the catalytic activity applied in borrowing hydrogen catalysis using ligands containing functional groups such as NH [33][34][35][36][37] and OH [38][39][40] . Among them, NNN ligands [41][42][43] bearing NH [44,45] coordinated with Ru metal could be potential chelating ligands due to their synthetic accessibility and excellent air-and moisture-stability compared to phosphine ligands.…”

Section: Introductionmentioning

confidence: 99%

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

Huang

Hong

Sun

et al. 2020

Applied Organom Chemis

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Six tridentate NNN ligand precursors derived from 2‐(pyridin‐2‐yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron‐donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high‐resolution mass spectroscopy, and Fourier transform infrared (FT‐IR). The molecular structures of 1f, 2a, and 2f have been determined by X‐ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five‐membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α‐alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru‐H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.

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Chemoselective Reactions of Functionalized Sulfonyl Halides

Liashuk,

Andriashvili,

Tolmachev

et al. 2023

The Chemical Record

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Chemoselective transformations of functionalized sulfonyl fluorides and chlorides are surveyed comprehensively. It is shown that sulfonyl fluorides provide an excellent selectivity control in their reactions. Thus, numerous conditions are tolerated by the SO2F group – from amide and ester formation to directed ortho‐lithiation and transition‐metal‐catalyzed cross‐couplings. Meanwhile, sulfur (VI) fluoride exchange (SuFEx) is also compatible with numerous functional groups, thus confirming its title of “another click reaction”. On the contrary, with a few exceptions, most transformations of functionalized sulfonyl chlorides typically occur at the SO2Cl moiety.

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Hydrogenation of nitroaromatics to anilines catalyzed by air‐stable arene ruthenium (II)–NNN pincer complexes

Cited by 8 publications

References 34 publications

Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

Chemoselective Reactions of Functionalized Sulfonyl Halides

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Hydrogenation of nitroaromatics to anilines catalyzed by air‐stable arene ruthenium (II)–NNN pincer complexes

Cited by 8 publications

References 34 publications

Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds

Ru(II)‐PBTNNXN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

Chemoselective Reactions of Functionalized Sulfonyl Halides

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Product

Resources

About

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols