Coordination chemistry of mononuclear ruthenium complexes bearing versatile 1,8-naphthyridine units: Utilization of specific reaction sites constructed by the secondary coordination sphere

Oyama, Dai; Abe, Ryosuke; Takase, Tsugiko

doi:10.1016/j.ccr.2017.11.024

Cited by 11 publications

(3 citation statements)

References 74 publications

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“…During the course of our studies on metal complexes featuring silyl multidentate ligands, , we have recently synthesized dirhodium complex C bearing a silyl-1,8-naphthyridine-based Si , N -ligand (abbreviated as napySi) (Figure c) . Due to the strong trans influence of the silyl ligand, C has a vacant coordination site (a Lewis acidic center) trans to the silyl moiety on each metal center, which is adjacent to a lone pair on the uncoordinated nitrogen atom of the naphthyridine moiety . Complex C reacted with BH 3 ·SMe 2 by capturing BH 3 with its nitrogen lone pair and weakening the B–H bonds on the rhodium center (Figure c) .…”

Section: Introductionmentioning

confidence: 99%

Iridium Complexes with a Naphthyridine-Based Si,N-Ligand: Synthesis and Catalytic Activity toward Olefin Hydrogenation

et al. 2022

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16-Electron iridium complexes bearing a silyl-1,8-naphthyridine-based bidentate ligand (napySi), Ir(κ2 Si,N-napySi)(H)(coe)X [X = Cl (1) and Me (2)], were synthesized and characterized. Single-crystal X-ray diffraction studies revealed that both 1 and 2 have a square-pyramidal geometry with the silyl moiety occupying the apical position and the nitrogen lone pair of napySi adjacent to the vacant metal center. Methyl complex 2 catalyzed hydrogenation of alkenes with H2 (1 atm) at room temperature. This hydrogenation proceeded significantly faster than that catalyzed by a related complex with no nitrogen lone pair adjacent to the metal. Based on this result, we suggest a possible catalytic cycle including cooperative activation of H2 between the nitrogen lone pair and the metal center for this system.

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Section: Introductionmentioning

confidence: 99%

Iridium Complexes with a Naphthyridine-Based Si,N-Ligand: Synthesis and Catalytic Activity toward Olefin Hydrogenation

et al. 2022

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“…The medicinal properties of naphthyridines and their derivatives are the major driving forces to synthesize them on a large scale. Among naphthyridines, 1,8-naphthyridines ( 1 , Figure A) and their derivatives are used as drugs for antimicrobial activities (nalidixic acid, 2 ), − HIV inhibitor ( 3 ), antibacterial activities (gemifloxacin, 4 ), , antitumor activity (vosaroxin, 5 ), etc. − The 1,8-naphthyridine derivatives can also act as monodentate, bidentate, or binucleating bridging ligands ( 6 , Figure A). − They also exhibit excellent thermally activated delayed fluorescence (TADF) and high photoluminescence quantum yield ( 7 ), which make them suitable blue organic light-emitting diodes (OLEDs). It is worth mentioning that the extensively substituted 1,8-naphthyridines and less substituted ones are used as probes to monitor the structure and function of enzymes and proteins.…”

Section: Introductionmentioning

confidence: 99%

Gram-Scale Synthesis of 1,8-Naphthyridines in Water: The Friedlander Reaction Revisited

et al. 2021

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The products of the Friedlander reaction, i.e., 1,8-naphthyridines, have far-reaching impacts in materials science, chemical biology, and medicine. The reported synthetic methodologies elegantly orchestrate the diverse synthetic routes of naphthyridines but require harsh reaction conditions, organic solvents, and expensive metal catalysts. Here, we introduce gram-scale synthesis of 1,8-naphthyridines in water using an inexpensive and biocompatible ionic liquid (IL) as a catalyst. This is the first-ever report on the synthesis of naphthyridines in water. This is a one-step reaction, and the product separation is relatively easy. The choline hydroxide (ChOH) is used as a metal-free, nontoxic, and water-soluble catalyst. In comparison to other catalysts reported in the literature, ChOH has the advantage of forming an additional hydrogen bond with the reactants, which is the vital step for the reaction to happen in water. Density functional theory (DFT) and noncovalent interaction (NCI) plot index analysis provide the plausible reaction mechanism for the catalytic cycle and confirm that hydrogen bonds with the IL catalyst are pivotal to facilitate the reaction. Molecular docking and molecular dynamics (MD) simulations are also performed to demonstrate the potentialities of the newly synthesized products as drugs. Through MD simulations, it was established that the tetrahydropyrido derivative of naphthyridine (10j) binds to the active sites of the ts3 human serotonin transporter (hSERT) (PDB ID: 6AWO) without perturbing the secondary structure, suggesting that 10j can be a potential preclinical drug candidate for hSERT inhibition and depression treatment.

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“…">Synthesis and Structure of ComplexesUnlike unsubstituted 2,2'-bipyridine and 1,10-phenanthroline, the pynp ligand has no C2 symmetry axis (Chart 1), so metal complexes containing pynp(s) may have several diastereomers. We previously reported that for ruthenium carbonyl complexes containing both bpy and pynp, formation of the desired isomers can be controlled by the order of introduction of the two ligands [18,20]. Using this method, dicarbonylruthenium complexes containing both pynp and phen were successfully prepared.…”

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Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

et al. 2019

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The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl–ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved.

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Coordination chemistry of mononuclear ruthenium complexes bearing versatile 1,8-naphthyridine units: Utilization of specific reaction sites constructed by the secondary coordination sphere

Cited by 11 publications

References 74 publications

Iridium Complexes with a Naphthyridine-Based Si,N-Ligand: Synthesis and Catalytic Activity toward Olefin Hydrogenation

Iridium Complexes with a Naphthyridine-Based Si,N-Ligand: Synthesis and Catalytic Activity toward Olefin Hydrogenation

Gram-Scale Synthesis of 1,8-Naphthyridines in Water: The Friedlander Reaction Revisited

Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

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