Beyond Metal-Arenes: Monocarbonyl Ruthenium(II) Catalysts for Transfer Hydrogenation Reactions in Cancer Cells DOI Creative Commons
Denise Lovison,

Tobias Berghausen,

Sophie R. Thomas

et al.

Published: May 12, 2023

With the aim to design new water-soluble organometallic Ru(II) complexes acting as anticancer agents catalysing transfer hydrogenation (TH) reactions with biomolecules, we have synthesized four monocarbonyl (1-4) featuring 1,4-bis(diphenylphosphino)butane (dppb) ligand and different bidentate nitrogen (N^N) ligands, of general formula [Ru(OAc)CO(dppb)(N^N)]n (n = +1, 0; OAc acetate). The compounds been characterised by methods, including 1H 31P NMR spectroscopy, electrochemistry well single crystals X-ray diffraction in case 1 4. also studied for their hydrolysis aqueous environment, catalytic regioselective reduction NAD+ 1,4-NADH solution sodium formate hydride source. Moreover, stoichiometric oxidation investigated UV-Visible spectrophotometry spectroscopy. Overall, initial structure-activity relationships could be inferred which point towards influence extension aromatic N^N cationic 1-3 on TH both reduction/oxidation processes. neutral complex 4, a picolinamidate ligand, stands out most active catalyst NAD+, while being completely inactive NADH oxidation. compound can convert pyruvate into lactate presence formate, albeit scarce efficiency. In any case, all compounds, intermediates observed even isolated 1-3. Together, insight from kinetic electrochemical characterization suggests that, 1-3, sees H-transfer rate limiting step, whereas H-donor, step is ruthenium substrate. latter further modulated di-cationic aquo- or mono-cationic hydroxo-species Instead, stable respect solution, appears operate via mechanism. Finally, activity ability form reactive oxygen species (ROS) cancerous non-tumorigenic cells vitro. Noteworthy, conversion aldehydes alcohols achieved three catalysts living cells, assessed fluorescence microscopy. Furthermore, formation intermediate upon treatment cancer cell extracts 3 has detected this study paves way application non-arene based biological environment.

Language: Английский

Well-Defined Robust Imidazole-Based Metal–Ligand Cooperative Ru(II)-para-Cymene for Transfer Hydrogenation of Furanic Aldehydes Using Renewable Alcohols DOI
Rahul Daga Patil, Sanjay Pratihar

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(16), P. 6206 - 6219

Published: April 9, 2024

The present study addresses the challenges in catalytic transfer hydrogenation using methanol/ethanol for converting biomass-derived furanic aldehydes to furfuryl alcohols. introduction of air-stable Ru(II)-para-cymene catalysts with imidazole-based metal–ligand cooperativity represents a significant advancement. Spectroscopic, situ monitoring, labeling, and DFT investigations reveal mechanistic details, highlighting role Ru–H generation through dehydrogenation Ru(II)-alkoxide intermediates. Hydride proton transfers are facilitated by interconvertible coordination mode imidazole Ru(II)–para-cymene, which is crucial maintaining catalyst's efficiency selectivity. Notably, pKa N–H coordinated significantly influences reactivity, following specific order depending on attached heterocycle: > pyridine thiazole. This correlates well computed activation barrier generation. catalyst exhibits ease synthesis, stability air moisture, use renewable hydrogen sources, excellent selectivity aldehydes, applicability various potential large-scale processes. These features collectively contribute economic sustainable nature both protocol, providing valuable contribution field hydrogenation.

Language: Английский

Citations

6
Beyond Metal-Arenes: Monocarbonyl Ruthenium(II) Catalysts for Transfer Hydrogenation Reactions in Water and in Cells DOI
Denise Lovison,

Tobias Berghausen,

Sophie R. Thomas

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 10798 - 10823

Published: Aug. 1, 2023

With the aim to design water-soluble organometallic Ru(II) complexes acting as anticancer agents catalyzing transfer hydrogenation (TH) reactions with biomolecules, we have synthesized four monocarbonyl (1–4), featuring 1,4-bis(diphenylphosphino)butane (dppb) ligand and different bidentate nitrogen (N∧N) ligands, of general formula [Ru(OAc)CO(dppb)(N∧N)]n (n = +1, 0; OAc acetate). The compounds been characterized by methods, including 1H 31P NMR spectroscopies, electrochemistry, well single-crystal X-ray diffraction in case 1 4. also studied for their hydrolysis an aqueous environment catalytic regioselective reduction nicotinamide adenine dinucleotide (NAD+) 1,4-dihydronicotinamide (1,4-NADH) solution sodium formate a hydride source. Moreover, stoichiometric oxidation 1,4-NADH investigated UV–visible spectrophotometry spectroscopy. results suggest that cycle can start directly from intact compound or its aquo/hydroxo species (in 1–3) afford ruthenium complex. Overall, initial structure–activity relationships could be inferred which point toward influence extension aromatic N∧N cationic 1–3 on TH both reduction/oxidation processes. While complex 3 is most active NADH O2, neutral 4, picolinamidate ligand, stands out catalyst NAD+, while being completely inactive oxidation. convert pyruvate into lactate presence formate, albeit scarce efficiency. In any case, all compounds, intermediates observed even isolated 1–3. Together, insights kinetic electrochemical characterization that, 1–3, sees H-transfer rate-limiting step, whereas NAD+ H-donor, step substrate, suggested density functional theory (DFT) calculations. Compound stable respect solution, appears operate via mechanism other derivatives. Finally, activity ability form reactive oxygen (ROS) cancerous nontumorigenic cells vitro. Noteworthy, conversion aldehydes alcohols achieved three catalysts living cells, assessed fluorescence microscopy. Furthermore, formation intermediate upon treatment cancer cell extracts has detected this study paves way application non-arene-based biological environment.

Language: Английский

Citations

12
Efficient and selective catalytic hydrogenation of furanic aldehydes using well defined Ru and Ir pincer complexes DOI
Rosa Padilla, Sakhitha Koranchalil, Martin Nielsen

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(20), P. 6767 - 6772

Published: Jan. 1, 2020

Homogeneous catalyzed hydrogenation of furanic aldehydes to their corresponding alcohols using PNP complexes.

Language: Английский

Citations

32
Deep eutectic solvents as H2-sources for Ru(II)-catalyzed transfer hydrogenation of carbonyl compounds under mild conditions DOI
Marzia Cavallo, Davide Arnodo, Alberto Mannu

et al.

Tetrahedron, Journal Year: 2021, Volume and Issue: 83, P. 131997 - 131997

Published: Feb. 9, 2021

Language: Английский

Citations

23
Manipulation of Charged Porous Cages as Tunable Platforms for Strong Gas Adsorption DOI
Meaghan M. Deegan,

Alexandra M. Antonio,

Kyle J. Korman

et al.

Chemistry of Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

Language: Английский

Citations

0
Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells DOI
Denise Lovison, Dario Alessi, Lorenzo Allegri

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(33)

Published: April 8, 2022

The chiral cationic complex [Ru(η

Language: Английский

Citations

14
Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2(η6-arene)P] (P = monophosphine) and [Rh(PP)2]X (PP = diphosphine, X = Cl−, BF4−) Complexes DOI Open Access
Alberto Mannu, Arnald Grabulosa, Salvatore Baldino

et al.

Catalysts, Journal Year: 2020, Volume and Issue: 10(2), P. 162 - 162

Published: Feb. 1, 2020

The reduction of ketones through homogeneous transfer hydrogenation catalyzed by transition metals is one the most important routes for obtaining alcohols from carbonyl compounds. interest this method increases when opportune catalytic precursors are able to perform transformation in an asymmetric fashion, generating enantiomerically enriched chiral alcohols. This reaction has been extensively studied terms catalysts and variety substrates. A large amount information about possible mechanisms available nowadays, which high importance development systems with excellent outcomes conversion, enantioselectivity Turn Over Frequency. On other side, many mechanistic aspects still unclear, especially those have shown only moderate performances hydeogenation. case neutral [RuCl2(η6-arene)(P)] cationic [Rh(PP)2]X (X = anion; P PP mono- bidentate phosphine, respectively) complexes. Herein, a summary known Transfer Hydrogenation these complexes provided continuous focus on more relevant features.

Language: Английский

Citations

19
Cationic carboxylate and thioacetate ruthenium(ii) complexes: synthesis and cytotoxic activity against anaplastic thyroid cancer cells DOI
Denise Lovison, Lorenzo Allegri, Federica Baldan

et al.

Dalton Transactions, Journal Year: 2020, Volume and Issue: 49(24), P. 8375 - 8388

Published: Jan. 1, 2020

High cytotoxic and antimetastatic activities against anaplastic thyroid cancer are displayed by cationic complexes [RuX(CO)(dppb)(phen)]Y (X = Y OAc, OPiv, SAc, NCS; X Cl PF6).

Language: Английский

Citations

13
Valorization of biomass-derived furans over molecular catalysts DOI Creative Commons
Ambikesh D. Dwivedi, Bhanu Priya,

Ramkrishna Chinthala

et al.

Tetrahedron Green Chem, Journal Year: 2023, Volume and Issue: 1, P. 100008 - 100008

Published: Jan. 1, 2023

The development of effective methodologies for the sustainable production chemicals and biofuels from lignocellulosic biomass has attracted immense attention scientific community. However, it is challenging due to highly complex nature sources. Over past few decades, numerous reports targeting various catalytic transformation reactions highlighting vital role catalysts in substrate activation product selectivity have appeared literature. Through this perspective, we present recent advances metal complexes-based molecular catalysis transforming biomass-derived 5-hydroxymethylfurfural (5-HMF) furfural (FAL) industrially important chemicals, materials, pharmaceuticals, biofuels. This article focuses on 5-HMF FAL involving hydrogenation, ring opening, hydrogenolysis, oxidation, amination over catalysts, provide insights into systems explored allied areas.

Language: Английский

Citations

5
Preparation of Neutral trans - cis [Ru(O2CR)2P2(NN)], Cationic [Ru(O2CR)P2(NN)](O2CR) and Pincer [Ru(O2CR)(CNN)P2] (P = PPh3, P2 = diphosphine) Carboxylate Complexes and their Application in the Catalytic Carbonyl Compounds Reduction DOI Creative Commons
Salvatore Baldino, Steven Giboulot, Denise Lovison

et al.

Organometallics, Journal Year: 2021, Volume and Issue: 40(8), P. 1086 - 1103

Published: April 14, 2021

The diacetate complexes trans-[Ru(κ1-OAc)2(PPh3)2(NN)] (NN = ethylenediamine (en) (1), 2-(aminomethyl)pyridine (ampy) (2), 2-(aminomethyl)pyrimidine (ampyrim) (3)) have been isolated in 76–88% yield by reaction of [Ru(κ2-OAc)2(PPh3)2] with the corresponding nitrogen ligands. ampy-type derivatives 2 and 3 undergo isomerization to thermodynamically most stable cationic [Ru(κ1-OAc)(PPh3)2(NN)]OAc (2a 3a) cis-[Ru(κ1-OAc)2(PPh3)2(NN)] (2b 3b) methanol at RT. trans-[Ru(κ1-OAc)2(P2)2] (P2 dppm (4), dppe (5)) compounds synthesized from suitable diphosphine toluene 95 °C. complex cis-[Ru(κ1-OAc)2(dppm)(ampy)](6) has obtained reflux ampy. trans-[Ru(κ1-OAc)2P2(NN)] (7–16; NN en, ampy, ampyrim, 8-aminoquinoline; P2 dppp, dppb, dppf, (R)-BINAP) can be easily a treatment ligands Alternatively these prepared trans-[Ru(OAc)2(PPh3)2(NN)] MEK 50 use (R)-BINAP affords trans-[Ru(κ1-OAc)2((R)-BINAP)(NN)] ampy (11), ampyrim (15)) as single stereoisomers. Treatment 8–15 RT leads [Ru(κ2-OAc)P2(NN)]OAc (8a–15a; ampyrim; (R)-BINAP). Similarly 2, dipivalate trans-[Ru(κ1-OPiv)2(PPh3)2(ampy)] (18) is [Ru(κ2-OPiv)2(PPh3)2] (17) CHCl3. pincer acetate [Ru(κ1-OAc)(CNNOMe)(PPh3)2] (19) HCNNOMe ligand 2-propanol NEt3 reflux. In addition, dppb [Ru(κ1-OAc)(CNN)(dppb)] (CNN AMTP (20), AMBQPh (21)) [Ru(κ2-OAc)2(PPh3)2], HAMTP or HAMBQPh NEt3, respectively. are active transfer hydrogenation H2 carbonyl S/C values up 10000 TOF 160000 h–1.

Language: Английский

Citations

9