New Dipyridylamine Ruthenium Complexes for Transfer Hydrogenation of Aryl Ketones in Water

Romain, Charles; Gaillard, Sylvain; Elmkaddem, Mohammed Kamal; Toupet, Loı̈c; Fischmeister, Cédric; Thomas, Christophe M.; Renaud, Jean‐Luc

doi:10.1021/om100127f

Cited by 62 publications

(47 citation statements)

References 31 publications

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“…The complex 3 adopts a pseudo-octahedral piano-stool geometry (Figure 4), known to be a typical one for the half-sandwich Ru(II) complexes, including the recently reported complex [Ru(η 6 -p-cym)(dpa)Cl]PF6 (1 in this work; [10]), whose structural parameters were included in Table 3 for comparative purposes. The Ru-N and Ru-Cg bond lengths are comparable for the chlorido (1; [10]) and iodido (3) complexes (Table 3); Cg = the centroid of the p-cymene aromatic ring.…”

Section: Single Crystal X-ray Analysismentioning

confidence: 98%

“…For this purpose, we chose the easily-obtainable [Ru(η 6 -p-cym)(dpa)Cl]PF6 complex ( Figure 1) [10], recently reported as having moderate, and thus possibly tunable, in vitro cytotoxicity against the MCF-7 cancer cells (IC50 = 40.8 μM) [11]. From the coordination chemistry point of view, this is the first report on Ru(II) complexes containing the VP ligand.…”

Section: Trans-[pt(dach)(ox)(vp)2] (Ic50 = 13 μM) Significantly Excementioning

confidence: 99%

“…The synthesis of the herein used complex [Ru(η 6 -p-cym)(dpa)Cl] + was reported in the literature, but with different reaction conditions (4 h/ambient temperature [15], 4 h/reflux [11], 6 h/reflux [16] or overnight stirring/50 °C [10]). In this work, the reaction time was considerably shortened to only 1 min, by using a microwave reactor.…”

Section: Synthesis and General Propertiesmentioning

confidence: 99%

“…Recently, the preparation [10,11,15,16], X-ray structure [10] and in vitro cytotoxicity [11] of the simple ruthenium(II) complex [Ru(η 6 -p-cym)(dpa)Cl]PF 6 were reported. In this work, its structure was modified by either different halogenido ligands (bromido or iodido) or monodentate O-coordinated carboxylato ligands (valproato or 4-phenylbutyrato).…”

Section: Synthesis and General Propertiesmentioning

confidence: 99%

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Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

et al. 2016

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Halogenido and carboxylato Ru(II) half-sandwich complexes of the general composition [Ru(η 6 -p-cym)(dpa)X]PF 6 (1-5) were prepared and thoroughly characterized with various techniques (e.g., mass spectrometry, NMR spectroscopy and X-ray analysis); dpa = 2,2 -dipyridylamine; p-cym = p-cymene; X = Cl − (for 1), Br − (for 2), I − (for 3), valproate(1−) (for 4) or 4-phenylbutyrate(1−) (for 5). A single-crystal X-ray analysis showed a pseudo-octahedral piano-stool geometry of [Ru(η 6 -p-cym)(dpa)I]PF 6 (3), with a η 6 -coordinated p-cymene, bidentate N-donor dpa ligand and iodido ligand coordinated to the Ru(II) atom. The results of the 1 H-NMR solution behaviour studies proved that the complexes 1-5 hydrolyse were in the mixture of solvents used (10% MeOD-d 4 /90% D 2 O). Complexes 1-5 were in vitro inactive against the A2780 human ovarian carcinoma cell line, up to the highest tested concentration (IC 50 > 100 µM).

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Section: Single Crystal X-ray Analysismentioning

confidence: 98%

Section: Trans-[pt(dach)(ox)(vp)2] (Ic50 = 13 μM) Significantly Excementioning

confidence: 99%

Section: Synthesis and General Propertiesmentioning

confidence: 99%

Section: Synthesis and General Propertiesmentioning

confidence: 99%

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Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

et al. 2016

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“…From here, the Ru−H bond is formed via a higher energy transition state (TS). The energetics of this process and for CO 2 elimination for the formate adducts of the bn complexes {(bn)Ru(MsEn)} + (10), {(bn)Ru(TsEn)} + (11), and {(bn)-Ru(TfEn)} + (12) and for the formate adduct of the hmb complex {(hmb)Ru(MsEn)} + (4) are collected in Table 4. (6) shows an asymmetric unit containing three crystallographically independent molecules.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺

et al. 2012

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A series of neutral Ru II half-sandwich complexes of the type [(η 6 -arene)Ru(N,N′)Cl] where the arene is para-cymene (p-cym), hexamethylbenzene (hmb), biphenyl (bip), or benzene (bn) and N,N′ is N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), N-(2-aminoethyl)-4-toluenesulfonamide (TsEn), or N-(2-aminoethyl)-methylenesulfonamide (MsEn) were synthesized and characterized. X-ray crystal structures of [(p-cym) The coordination of formate and subsequent CO 2 elimination to generate the hydride were modeled computationally by density functional theory (DFT). CO 2 elimination occurs via a two-step process with the coordinated formate first twisting to present its hydrogen toward the metal center. The computed barriers for CO 2 release for arene = benzene follow the order MsEn > TsEn > TfEn, and for the MsEn system the barrier followed bn < hmb, both consistent with the observed rates. The effect of methanol on transfer hydrogenation rates in aqueous solution was investigated. A study of pH dependence of the reaction in D 2 O gave the optimum pH* as 7.2 with a TOF of 1.58 h −1 for 2. The series of compounds reported here show an improvement in the catalytic activity by an order of magnitude compared to the ethylenediamine analogues. ■ INTRODUCTIONThe coenzyme nicotinamide adenine dinucleotide (NAD + ) and its reduced form 1,4-NADH have crucial roles in many cellular metabolic processes such as regulation of energy metabolism, antioxidative function, DNA repair and transcription, immunological functions, and cell death. 1 The coenzymes are involved in many other processes, acting as substrates and cofactors for enzymes such as NAD + ligases, oxidoreductases, polymerases, and deacetylases involved in biosynthesis.The coenzymes NAD + /NADH have been studied intensively during the past few years. It has been demonstrated that changes in metabolism result in fluctuations in the ratio NAD + / NADH or, conversely, changes in the ratio can produce metabolic changes. 2 In some cases alterations in the cellular redox status have been shown to play an important role in cell death, and therefore the coenzymes have become possible drug targets for chronic or autoimmune diseases such as Parkinson's, hepatitis C, diabetic vascular dysfunction, hyperglycemia, and cancer. 3 The concentration of NAD + and the ratio NAD + /NADH have been shown to be very important for cancer cells. On the one hand, due to their active metabolism, cancer cells generate high levels of oxidizing species and, therefore, they are under constant oxidative stress. 4 This makes cancer cells more dependent on redox regulatory systems and more sensitive to variations in the NAD + /NADH ratio. On the other hand, NAD + is required as a substrate for many enzymatic reactions such as ADP-ribosylation, which is crucial for genome stability and DNA repair. 3 Due to the up-regulation of some enzymes required for the biosynthesis of NAD + in cancer cells, a

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Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well‐Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands

Yamaguchi

Fujita

2014

Ligand Platforms in Homogenous Catalytic Reactions With Metals

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New Dipyridylamine Ruthenium Complexes for Transfer Hydrogenation of Aryl Ketones in Water

Cited by 62 publications

References 31 publications

Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺

Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well‐Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands

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New Dipyridylamine Ruthenium Complexes for Transfer Hydrogenation of Aryl Ketones in Water

Cited by 62 publications

References 31 publications

Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

Half-Sandwich Ru(II) Halogenido, Valproato and 4-Phenylbutyrato Complexes Containing 2,2′-Dipyridylamine: Synthesis, Characterization, Solution Chemistry and In Vitro Cytotoxicity

Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD+

Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well‐Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands

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Improved Catalytic Activity of Ruthenium–Arene Complexes in the Reduction of NAD⁺