Highly efficient Ru(ii)–alkylidene based Hoveyda–Grubbs catalysts for ring-closing metathesis reactions

Three novel phosphine-free Ru-alkylidenes (7a–7c) have been synthesized and utilized as efficient catalysts for ring closing metathesis (RCM) reaction. Spectroscopic data, i.e. NMR and HRMS, along with single crystal X-ray diffraction analysis, were used to confirm their chemical structures. The tosylated carbenoid 7b showed the highest efficiency in cyclizing different acyclic diene substrates. RCM of various (un)substituted N,N-diallylaniline derivatives and stereoselective RCM of different macromolecular dienes were well tolerated using only a catalytic amount (0.5–2.0 mol%) of the additive catalyst (7b) as compared to the well-known Grubbs (II) and Hoveyda–Grubbs (II) catalysts.

Three novel phosphine-free Ru-alkylidenes (7a–7c) have been synthesized and utilized as efficient catalysts for ring closing metathesis (RCM) reaction.     

Poly[2,2′-(4,4′-bipyridine)-5,5′-bibenzimidazole] functionalization of carbon black for improving the oxidation stability and oxygen reduction reaction of fuel cells

The rapid oxidation of carbon black (CB) is a major drawback for its use as a catalyst support in polymer electrolyte fuel cells. Here, we synthesize poly[2,2′-(4,4′-bipyridine)-5,5′-bibenzimidazole] (BiPyPBI) as a conducting polymer and use it to functionalize the surface of CB and homogenously anchor platinum metal nanoparticles (Pt-NPs) on a CB surface. The as-prepared materials were confirmed by different spectroscopic techniques, including nuclear magnetic resonance spectroscopy, energy-dispersive X-ray, thermal gravimetric analysis, and scanning-transmittance microscopy. The as-fabricated polymer-based CB catalyst showed an electrochemical surface area (ECSA) of 63.1 cm² mg_Pt⁻¹, giving a catalyst utilization efficiency of 74.3%. Notably, the BiPyPBI-based CB catalyst exhibited remarkable catalytic activity towards oxygen reduction reactions. The onset potential and the diffusion-limiting current density reached 0.66 V and 5.35 mA cm⁻², respectively. Furthermore, oxidation stability testing showed a loss of only 16% of Pt-ECSA for BiPyPBI-based CB compared to a 36% loss of Pt-ECSA for commercial Pt/CB after 5000 potential cycles. These improvements were related to the synergetic effect between the nitrogen-rich BiPyPBI polymer, which promoted the catalytic activity through the structural nitrogen atoms, and demolished the degradation of CB via the wrapping process.

The rapid oxidation of carbon black (CB) is a major drawback for its use as a catalyst support in polymer electrolyte fuel cells.     

Reactive molecular dynamics simulation of the high-temperature pyrolysis of 2,2′,2′′,4,4′,4′′,6,6′,6′′-nonanitro-1,1′:3′,1′′-terphenyl (NONA)

2,2′,2′′,4,4′,4′′,6,6′,6′′-Nonanitro-1,1′:3′,1′′-terphenyl (NONA) is currently recognized as an excellent heat-resistant explosive. To improve the atomistic understanding of the thermal decomposition paths of NONA, we performed a series of reactive force field (ReaxFF) molecular dynamics simulations under extreme conditions of temperature and pressure. The results show that two distinct initial decomposition mechanisms are the homolytic cleavage of the C–NO₂ bond and nitro–nitrite (NO₂ → ONO) isomerization followed by NO fission. Bimolecular and fused ring compounds are found in the subsequent decomposition of NONA. The product identification analysis under finite time steps showed that the gaseous products are CO₂, N₂, and H₂O. The amount of CO₂ is energetically more favorable for the system at high temperature or low density. The carbon-containing clusters are a favorable growth pathway at low temperatures, and this process was further demonstrated by the analysis of diffusion coefficients. The increase of the crystal density accelerates the decomposition of NONA judged by the analysis of reaction kinetic parameters and activation barriers. In the endothermic and exothermic stages, a 20% increase in NONA density increases the activation energies by 3.24 and 0.48 kcal mol⁻¹, respectively. The values of activation energies (49.34–49.82 kcal mol⁻¹) agree with the experimental data in the initial decomposition stage.

The bimolecular and fused ring compounds are found in the high-temperature pyrolysis of NONA using ReaxFF molecular dynamics simulations.     

Back to the future: asymmetrical DπA 2,2′-bipyridine ligands for homoleptic copper(i)-based dyes in dye-sensitised solar cells

Metal complexes used as sensitisers in dye-sensitised solar cells (DSCs) are conventionally constructed using a push–pull strategy with electron-releasing and electron-withdrawing (anchoring) ligands. In a new paradigm we have designed new DπA ligands incorporating diarylaminophenyl donor substituents and phosphonic acid anchoring groups. These new ligands function as organic dyes. For two separate classes of DπA ligands with 2,2′-bipyridine metal-binding domains, the DSCs containing the copper(i) complexes [Cu(DπA)₂]⁺ perform better than the push–pull analogues [Cu(DD)(AA)]⁺. Furthermore, we have shown for the first time that the complexes [Cu(DπA)₂]⁺ perform better than the organic DπA dye in DSCs. The synthetic studies and the device performances are rationalised with the aid of density functional theory (DFT) and time-dependent DFT (TD-DFT) studies.

Two homoleptic copper(i) complexes with [Cu(DπA)₂]⁺ design have been studied as sensitisers in DSCs and are superior to the DπA ligands and related heteroleptic complexes as dyes.     

Heterogeneous water oxidation photocatalysis based on periodic mesoporous organosilica immobilizing a tris(2,2′-bipyridine)ruthenium sensitizer

A periodic mesoporous organosilica (PMO) containing 2,2′-bipyridine groups (BPy-PMO) has been shown to possess a unique pore wall structure in which the 2,2′-bipyridine groups are densely and regularly packed. The surface 2,2′-bipyridine groups can function as chelating ligands for the formation of metal complexes, thus generating molecularly-defined catalytic sites that are exposed on the surface of the material. We here report the construction of a heterogeneous water oxidation photocatalyst by immobilizing several types of tris(2,2′-bipyridine)ruthenium complexes on BPy-PMO where they function as photosensitizers in conjunction with iridium oxide as a catalyst. The Ru complexes produced on BPy-PMO in this work were composed of three bipyridine ligands, including the BPy in the PMO framework and two X₂bpy, denoted herein as Ru(X)-BPy-PMO where X is H (2,2′-bipyridine), Me (4,4′-dimethyl-2,2′-bipyridine), t-Bu(4,4′-di-tert-butyl-2,2′-bipyridine) or CO₂Me (4,4′-dimethoxycarbonyl-2,2′-bipyridine). Efficient photocatalytic water oxidation was achieved by tuning the photochemical properties of the Ru complexes on the BPy-PMO through the incorporation of electron-donating or electron-withdrawing functionalities. The reaction turnover number based on the amount of the Ru complex was improved to 20, which is higher than values previously obtained from PMO systems acting as water oxidation photocatalysts.

Ruthenium complex photosensitizer fixed on 2,2′-bipyridine bridged-periodic mesoporous organosilica with iridium oxide exhibits an efficient photocatalytic water oxidation.     

Cobalt–carbon/silica nanocomposites prepared by pyrolysis of a cobalt 2,2′-bipyridine terephthalate complex for remediation of cationic dyes

Recently, carbon nanostructures have attracted interest because of their unique properties and interesting applications. Here, CoC@SiO₂-850 (3) and CoC@SiO₂-600 (4) cobalt–carbon/silica nanocomposites were prepared by solid-state pyrolysis of anthracene with Co(tph)(2,2′-bipy)·4H₂O (1) complex in the presence of silica at 850 and 600 °C, respectively, where 2,2′-bipy is 2,2′-bipyridine and tph is the terephthalate dianion. Moreover, Co(μ-tph)(2,2′-bipy) (2) was isolated and its X-ray structure indicated that cobalt(ii) has a distorted trigonal prismatic coordination geometry. 2 is a metal–organic framework consisting of one-dimensional zigzag chains within a porous grid network. 3 and 4 consist of cobalt(0)/cobalt oxide nanoparticles with a graphitic shell and carbon nanotubes embedded in the silica matrix. They were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS revealed that the nanocomposites are functionalized with oxygen-containing groups, such as carboxylic acid groups. In addition, the presence of metallic cobalt nanoparticles embedded in graphitized carbon was verified by XRD and TEM. The efficiency of 3 for adsorption of crystal violet (CV) dye was investigated by batch and column experiments. At 25 °C, the Langmuir adsorption capacity of 3 for CV was 214.2 mg g⁻¹ and the fixed-bed column capacity was 36.3 mg g⁻¹. The adsorption data were well fitted by the Freundlich isotherm and pseudo-second-order kinetic model. The adsorption process was spontaneous and endothermic.

A cobalt–carbon@silica nanocomposite was synthesized from a cobalt 2,2′-bipyridine terephthalate complex and its adsorption behavior towards crystal violet dye was tested using batch and column techniques.     

Convergent access to bis-1,2,4-triazinyl-2,2′-bipyridines (BTBPs) and 2,2′-bipyridines via a Pd-catalyzed Ullman-type reaction

Multidentate, soft-Lewis basic, complexant scaffolds have displayed significant potential in the discrete speciation of the minor actinides from the neutron-absorbing lanthanides resident in spent nuclear fuel. Efforts to devise convergent synthetic strategies to targets of interest to improve liquid–liquid separation outcomes continue, but significant challenges to improve solubility in process-relevant diluents to effectively define meaningful structure–activity relationships remain. In the current work, a synthetic method to achieve the challenging 2,2′-bipyridine bond of the bis-1,2,4-triazinyl-2,2′-bipyridine (BTBP) complexant class leveraging a Pd-catalyzed Ullman-type coupling is reported. This convergent strategy improves upon earlier work focused on linear synthetic access to the BTBP complexant moiety. Method optimization, relevant substrate scope and application, as well as a preliminary mechanistic interrogation are reported herein.

Access to functionalized BTBP complexants through a reductive coupling strategy decreases linearity of common synthetic strategies towards these relevant materials for separations.     

Fe(ii) and Mn(ii) removal by Ca(ii)–manganite (γ-MnOOH)-modified red mud granules in water

In this study, a material (DLRMG) was synthesized by modifying Ca²⁺ and manganite (γ-MnOOH) on red mud granules (RMG), which were the main raw materials derived from industrial alumina. Moreover, a series of experiments were conducted on the adsorption of Fe²⁺ and Mn²⁺ in underground water. The prepared samples were analyzed by X-ray diffraction (XRD), thermogravimetric analysis-differential thermal analysis (TG-DTA), zeta potential analysis, BET and scanning electron microscopy (SEM); the concentration of the effluent was found to be of acceptable standard after the treatment. DLRMG continued to treat fluoride wastewater even after the saturated adsorption of Fe²⁺ and Mn²⁺, and the results clearly showed that the treatment was effective. Overall, the problems of red mud stockpile and pollution in China would be effectively controlled by DLRMG.

The use of the waste of aluminum industry to prepare effective polluted materials for the treatment of underground water.     

Ru(ii)–N-heterocyclic carbene complexes: synthesis,characterization, transfer hydrogenation reactions and biological determination

A series of ruthenium(ii) complexes with N-heterocyclic carbene ligands were successfully synthesized by transmetalation reactions between silver(i) N-heterocyclic carbene complexes and [RuCl₂(p-cymene)]₂ in dichloromethane under Ar conditions. All new compounds were characterized by spectroscopic and analytical methods. These ruthenium(ii)–NHC complexes were found to be efficient precatalysts for the transfer hydrogenation of ketones by using 2-propanol as the hydrogen source in the presence of KOH as a co-catalyst. The antibacterial activity of ruthenium N-heterocyclic carbene complexes 3a–f was measured by disc diffusion method against Gram positive and Gram-negative bacteria. Compounds 3d exhibited potential antibacterial activity against five bacterial species among the six used as indicator cells. The product 3e inhibits the growth of all the six tested microorganisms. Moreover, the antioxidant activity determination of these complexes 3a–f, using 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azinobis-3-ethylbenzothiazoline-6-sulphonic acid (ABTS) as reagent, showed that compounds 3b and 3d possess DPPH and ABTS antiradical activities. From a concentration of 1 mg ml⁻¹, these two complexes presented a similar scavenging activity to that of the two used controls gallic acid (GA) and butylated hydroxytoluene (BHT). From a concentration of 10 mg ml⁻¹, the percentage inhibition of complexes 3b and 3d was respectively 70% and 90%. In addition, these two Ru–NHC complexes exhibited antifungal activity against Candida albicans. Investigation of the anti-acetylcholinesterase activity of the studied complexes showed that compounds 3a, 3b, 3d and 3e exhibited good activity at 100 μg ml⁻¹ and product 3d is the most active. In a cytotoxicity study the complexes 3 were evaluated against two human cancer cell lines MDA-MB-231 and MCF-7. Both 3d and 3e complexes were found to be active against the tested cell lines showing comparable activity with examples in the literature.

A series of ruthenium(ii) complexes with N-heterocyclic carbene ligands were successfully synthesized by transmetalation reactions between silver(i) N-heterocyclic carbene complexes and [RuCl₂(p-cymene)]₂ in dichloromethane under Ar conditions.     

P-stereocontrolled synthesis of oligo(nucleoside N3′→O5′ phosphoramidothioate)s – opportunities and limitations

3′-N-(2-Thio-1,3,2-oxathiaphospholane) derivatives of 5′-O-DMT-3′-amino-2′,3′-dideoxy-ribonucleosides (_NOTP-N), that bear a 4,4-unsubstituted, 4,4-dimethyl, or 4,4-pentamethylene substituted oxathiaphospholane ring, were synthesized. Within these three series, _NOTP-N differed by canonical nucleobases (i.e., Ade^Bz, Cyt^Bz, Gua^iBu, or Thy). The monomers were chromatographically separated into P-diastereomers, which were further used to prepare N_NPSN′ dinucleotides (3), as well as short P-stereodefined oligo(deoxyribonucleoside N3′→O5′ phosphoramidothioate)s (NPS-) and chimeric NPS/PO- and NPS/PS-oligomers. The condensation reaction for _NOTP-N monomers was found to be 5–6 times slower than the analogous OTP derivatives. When the 5′-end nucleoside of a growing oligomer adopts a C3′-endo conformation, a conformational ‘clash’ with the incoming _NOTP-N monomer takes place, which is a main factor decreasing the repetitive yield of chain elongation. Although both isomers of N_NPSN′ were digested by the HINT1 phosphoramidase enzyme, the isomers hydrolyzed at a faster rate were tentatively assigned the R_P absolute configuration. This assignment is supported by X-ray analysis of the protected dinucleotide ^DMTdG^iBu_NPSMeT_OAc, which is P-stereoequivalent to the hydrolyzed faster P-diastereomer of dG_NPST.

Separated P-diastereomers of 3′-N-(2-thio-1,3,2-oxathiaphospholane) derivatives of 5′-O-DMT-3′-amino-2′,3′-dideoxy-ribonucleosides were used to prepare P-stereodefined N_NPSN′ dinucleotides and short NPS-, NPS/PO- and NPS/PS-oligomers.     

DNA/lysozyme binding propensity and nuclease properties of benzimidazole/2,2′-bipyridine based binuclear ternary transition metal complexes

In the present contribution, new binuclear ternary complexes; [M₂(bpy)₄L](ClO₄)₄ (M = Co(ii) (1) and Ni(ii) (2); bpy = 2,2′-bipyridine; L = 1,1′-(hexane-1,6-diyl)bis[2-(pyridin-2-yl)1H-benzimidazole] and [Cu₂(bpy)₂(OH₂)₂L](BF₄)₄ (3) were synthesized, characterized and screened for their antimicrobial activity and cytotoxicity against human liver carcinoma cells (HepG-2) as well as non-malignant human embryonic kidney cells (HEK-293). The structural studies were complemented by density functional theory (DFT) calculations. DNA binding of 1–3 was spectrophotometrically studied. The DNA cleavage ability of 1–3 towards the supercoiled plasmid DNA (pBR322 DNA) was examined through gel electrophoresis. Compound 3 has the highest cytotoxic activity (IC₅₀ = 3.5 μg mL⁻¹) against HepG-2 among the investigated complexes and is non cytotoxic to noncancerous HEK-293. Complexes (1 and 2) exhibited toxicity to HEK-293 with IC₅₀ values of 30.3 and 23.5 μg mL⁻¹ in that order. While compound 1 showed antifungal activity against Cryptococcus neoformans, complex 2 exhibited its toxicity against Candida albicans.

The binuclear ternary transition metal complexes have the ability to bind to lysozyme and DNA as well as DNA cleavage. Complexes exhibited cytotoxicity to only the cancerous cells (HepG-2) and is safe to the non-malignant HEK-293.     

Experimental and DFT studies of sulfadiazine ‘piano-stool’ Ru(ii) and Rh(iii) complexes

While sulfadiazine (HL^SZ) is extensively used to elaborate complexes of intriguing biological applications (e.g. topical antibiotic silvadene; silver sulfadiazine), the molecular structure modification of sulfadiazine or even other sulfa drugs by coordination to either η⁶-cymene Ru(ii) or η⁵-Cp* Rh(iii) motif has not been investigated. Here, half-sandwich organoruthenium(ii) and organorhodium(iii) compounds of the type [(η⁶-p-cymene)Ru(L^SZ)₂] (1) and [(η⁵-C₅Me₅)Rh(L^SZ)₂] (2) are synthesized, characterized and evaluated for their potential antimicrobial activity. Spectroscopic and single crystal X-ray analysis showed that L^SZ is coordinated to Rh(iii) via both the sulfonamide and pyrimidine nitrogen atoms forming “piano-stool” geometry. In 2, the NMR equivalence clearly pointed to participation of two L^SZ molecules in a fluxional process in which the third bond of the base of the stool is oscillating between two equivalent sulfonamide nitrogen atoms. While 1 was biologically inactive, complex 2 was potent against Gram-positive bacteria, Candida albicans and Cryptococcus neoformans. Hen white egg lysozyme (HEWL), a model protein, reacted covalently with 2via the loss of one L^SZ molecule, while compound 1 decomposed during the interaction with that protein.

Binding of certain metal complexes to proteins may cause cytotoxicity. While [(η⁶-p-Cym)Ru(L^SZ)₂] decomposed during the reaction with hen white egg lysozyme, a Rh(iii) analogue was covalently bio-conjugated via the elimination of a sulfadiazine.     

Elucidating the intramolecular contrast in the STM images of 2,4,6-tris(4′,4′′,4′′′-trimethylphenyl)-1,3,5-triazine molecules recorded at room-temperature and at the liquid-solid interface

Star-shaped 2,4,6-tris(4′,4′′,4′′′-trimethylphenyl)-1,3,5-triazine molecules self-assemble at the solid–liquid interface into a compact hexagonal nanoarchitecture on graphite. High resolution scanning tunneling microscopy (STM) images of the molecules reveal intramolecular features. Comparison of the experimental data with calculated molecular charge density contours shows that the molecular features in the STM images correspond to molecular LUMO+2.

Intramolecular contrast in the STM images of 2,4,6-tris(4′,4′′,4′′′-trimethylphenyl)-1,3,5-triazine molecules recorded at room-temperature and at the liquid–solid interface.     

Four- and five-coordinate nickel(ii) complexes bearing new diphosphine–phosphonite and triphosphine–phosphite ligands: catalysts for N-alkylation of amines

The reaction of Ph₂PCH₂OH with PhPCl₂ and PCl₃ in the presence of Et₃N afforded new phosphonite compounds PhP(OCH₂PPh₂)₂1 and P(OCH₂PPh₂)₃2, respectively. The reaction between 1 and [NiCl₂(DME)] in dichloromethane gave the five-coordinate complex [NiCl₂(1-κ³P,P,P)] 3. Conversely, 1 reacts with [NiCl₂(DME)] in the presence of NH₄PF₆ in dichloromethane to yield the four coordinate ionic complex [NiCl(1-κ³P,P,P)][PF₆] 4. The reactions between 1, [NiCl₂(DME)] and KPF₆ in the presence of RNC (R = Xylyl, ^tBu and ⁱPr) in dichloromethane yielded the five coordinate monocationic [NiCl(1-κ³P,P,P)(RNC)][PF₆] (R = Xylyl) and dicationic [Ni(1-κ³P,P,P)(RNC)₂][PF₆]₂ (R = ^tBu and ⁱPr) complexes, respectively. The analogous reaction of 2 with [NiCl₂(DME)] in the presence of KPF₆ gave complex [NiCl(2-κ⁴P,P,P,P)][PF₆], 8. The structures of all complexes were determined by single crystal X-ray diffraction studies and supported by spectroscopic methods. To demonstrate their catalytic application, N-alkylation reactions between primary aryl amines, benzyl and 4-methoxy benzyl alcohols were found to proceed smoothly in the presence of 2.5 mol% of complexes bearing ligand 1 and <0.5 mmol of KOBu^t in toluene at 140 °C. The C–N coupled products were formed in very good yields. Its substrate scope includes sterically encumbered, heterocyclic amines and aliphatic alcohol.

A series of nickel(ii) complexes supported by the new tridentate P3 and tetradentate P4 ligands act efficiently as catalysts for the N-alkylation of primary amines with alcohols.     

Pharmacokinetics and Distribution over the Blood-Brain Barrier of Zalcitabine (2′,3′-Dideoxycytidine) and BEA005 (2′,3′-Dideoxy-3′-Hydroxymethylcytidine) in Rats, Studied by Microdialysis

Microdialysis was applied to sample the unbound drug concentration in the extracellular fluid in brain and muscle of rats given zalcitabine (2′,3′-dideoxycytidine; n = 4) or BEA005 (2′,3′-dideoxy-3′-hydroxymethylcytidine; n = 4) (50 mg/kg of body weight given subcutaneously). Zalcitabine and BEA005 were analyzed by high-pressure liquid chromatography with UV detection. The maximum concentration of zalcitabine in the dialysate (C_max) was 31.4 ± 5.1 μM (mean ± standard error of the mean) for the brain and 238.3 ± 48.1 μM for muscle. The time to C_max was found to be from 30 to 45 min for the brain and from 15 to 30 min for muscle. Zalcitabine was eliminated from the brain and muscle with half-lives 1.28 ± 0.64 and 0.85 ± 0.13 h, respectively. The ratio of the area under the concentration-time curve (AUC) (from 0 to 180 min) for the brain and the AUC for muscle (AUC ratio) was 0.191 ± 0.037. The concentrations of BEA005 attained in the brain and muscle were lower than those of zalcitabine, with C_maxs of 5.7 ± 1.4 μM in the brain and 61.3 ± 12.0 μM in the muscle. The peak concentration in the brain was attained 50 to 70 min after injection, and that in muscle was achieved 30 to 50 min after injection. The half-lives of BEA005 in the brain and muscle were 5.51 ± 1.45 and 0.64 ± 0.06 h, respectively. The AUC ratio (from 0 to 180 min) between brain and muscle was 0.162 ± 0.026. The log octanol/water partition coefficients were found to be −1.19 ± 0.04 and −1.47 ± 0.01 for zalcitabine and BEA005, respectively. The degrees of plasma protein binding of zalcitabine (11% ± 4%) and BEA005 (18% ± 2%) were measured by microdialysis in vitro. The differences between zalcitabine and BEA005 with respect to the AUC ratio (P = 0.481), half-life in muscle (P = 0.279), and level of protein binding (P = 0.174) were not statistically significant. The differences were statistically significant in the case of the half-life in the brain (P = 0.032), clearance (P = 0.046), volume of distribution (P = 0.027) in muscle, and octanol/water partition coefficient (P = 0.019).     

Heterodinuclear nickel(ii)–iron(ii) azadithiolates as structural and functional models for the active site of [NiFe]-hydrogenases

To develop the biomimetic chemistry of [NiFe]-H₂ases, the first azadithiolato-bridged NiFe model complexes [CpNi{(μ-SCH₂)₂NR}Fe(CO)(diphos)]BF₄ (5, R = Ph, diphos = dppv; 6, 4-ClC₆H₄, dppv; 7, 4-MeC₆H₄, dppv; 8, CO₂CH₂Ph, dppe; 9, H, dppe) have been synthesized via well-designed synthetic routes. Thus, treatment of RN[CH₂S(O)CMe]₂ with t-BuONa followed by reaction of the resulting intermediates RN(CH₂SNa)₂ with (dppv)Fe(CO)₂Cl₂ or (dppe)Fe(CO)₂Cl₂ gave the N-substituted azadithiolato-chelated Fe complexes [RN(CH₂S)₂]Fe(CO)₂(diphos) (1, R = Ph, diphos = dppv; 2, 4-ClC₆H₄, dppv; 3, 4-MeC₆H₄, dppv; 4, CO₂CH₂Ph, dppe). Further treatment of 1–4 with nickelocene in the presence of HBF₄·Et₂O afforded the corresponding N-substituted azadithiolato-bridged NiFe model complexes 5–8, while treatment of 8 with HBF₄·Et₂O resulted in formation of the parent azadithiolato-bridged model complex 9. While all the new complexes 1–9 were characterized by elemental analysis and spectroscopy, the molecular structures of model complexes 6–8 were confirmed by X-ray crystallographic study. In addition, model complexes 7 and 9 were found to be catalysts for H₂ production with moderate i_cat/i_p and overpotential values from TFA under CV conditions.

The first azadithiolato-bridged NiFe model complexes with a general formula [CpNi{(μ-SCH₂)₂NR}Fe(CO)(diphos)]BF₄ have been synthesized, characterized, and for some of them found to be catalysts for proton reduction to H₂ under CV conditions.     

Corroboration of Zn(ii)–Mg(ii)-tertiary structure interplays essential for the optimal catalysis of a phosphorothiolate thiolesterase ribozyme

The TW17 ribozyme, a catalytic RNA selected from a pool of artificial RNA, is specific for the Zn²⁺-dependent hydrolysis of a phosphorothiolate thiolester bond. Here, we describe the organic synthesis of both guanosine α-thio-monophosphate and the substrates required for selecting and characterizing the TW17 ribozyme, and for deciphering the catalytic mechanism of the ribozyme. By successively substituting the substrate originally conjugated to the RNA pool with structurally modified substrates, we demonstrated that the TW17 ribozyme specifically catalyzes phosphorothiolate thiolester hydrolysis. Metal titration studies of TW17 ribozyme catalysis in the presence of Zn²⁺ alone, Zn²⁺ and Mg²⁺, and Zn²⁺ and [Co(NH₃)₆]³⁺ supported our findings that Zn²⁺ is absolutely required for ribozyme catalysis, and indicated that optimal ribozyme catalysis involves the presence of outer-sphere and one inner-sphere Mg²⁺. A survey of the TW17 ribozyme activity at various pHs revealed that the activity of the ribozyme critically depends on the alkaline conditions. Moreover, a GNRA tetraloop-containing ribozyme constructed with active catalysis in trans provided catalysis and multiple substrate turnover efficiencies significantly higher than ribozymes lacking a GNRA tetraloop. This research supports the essential roles of Zn²⁺, Mg²⁺, and a GNRA tetraloop in modulating the TW17 ribozyme structure for optimal ribozyme catalysis, leading also to the formulation of a proposed reaction mechanism for TW17 ribozyme catalysis.

Zn(ii) and Mg(ii) and GAGA tetraloop in the ion atmosphere of the TW17 ribozyme is critical to optimal ribozyme catalysis at alkaline pH.     

Mo(vi) complexes of amide–imine conjugates for tuning the selectivity of fluorescence recognition of Y(iii) vs. Pb(ii)

Two amide–imine conjugates, viz. 3-methyl-benzoic acid (4-diethylamino-2-hydroxy-benzylidene)-hydrazide (L1) and 3-methyl-benzoic acid (2-hydroxy-naphthalen-1-ylmethylene)-hydrazide (L2), have been prepared and used for a further synthesis of Mo(vi) complexes (M1 and M2, respectively). Single crystal X-ray diffraction analysis confirmed their structures. Interestingly, M1 selectively recognizes Y³⁺ and Pb²⁺ at two different wavelengths, whereas M2 selectively interacts with Y³⁺ with a significantly high binding constant, 1.3 × 10⁵ M⁻¹. The proposed sensing mechanism involves the displacement of Mo(vi) by Y³⁺/Pb²⁺ from respective Mo(vi) complexes. The TCSPC experiment also substantiates the “turn-on” fluorescence process. A logic gate has been constructed utilizing the fluorescence recognition of cations by M1. DFT studies corroborated the cation–probe interactions and allowed exploring the orbital energy parameters.

Two amide–imine conjugates and their Mo(vi) complexes (M1 and M2) were characterized by single crystal X-ray diffraction analysis. While M1 recognises both Y³⁺ and Pb²⁺ at two different wavelengths, M2 recognises only Y³⁺ with significantly high binding constant.     

A theoretical study on the on–off phosphorescence of novel Pt(ii)/Pt(iv)–bisphenylpyridinylmethane complexes

An in-depth theoretical study on the Pt(ii)/Pt(iv)–bisphenylpyridinylmethane complexes was carried out, which focused on the geometric/electronic structures, excitation procedures, on–off phosphorescence mechanisms, and structure–optical performance relationships. The key roles of the linkages (LK) connected in the middle of phenylpyridines were carefully investigated using multiple wavefunction analysis methods, such as non-covalent interaction (NCI) visualizations and natural bond orbital (NBO) studies. The phosphorescence-off phenomenon was considered by hole–electron analysis and visualizations, spin–orbit coupling (SOC) studies, and NBO analysis. Through these investigations, the relationship of the substituents in LK and the optical performances were revealed, as well as the fundamental principles of the phosphorescence-quenching mechanism in Pt(iv) complexes, which pave the way for further performance/structural renovation works. In addition, an intuitive visualization method was developed using a heatmap to quantitatively express the SOC matrix elementary (SOCME), which is helpful for big data simplification for phosphorescence analysis.

An in-depth theoretical study on the Pt(ii)/Pt(iv)–bisphenylpyridinylmethane complexes was carried out, which focused on the structures, excitation procedures, on–off phosphorescence mechanisms, and structure–optical performance relationships.     

Divergent synthesis of flavones and flavanones from 2′-hydroxydihydrochalcones via palladium(ii)-catalyzed oxidative cyclization

Divergent and versatile synthetic routes to flavones and flavanones via efficient Pd(ii) catalysis are disclosed. These Pd(ii) catalyses expediently provide a variety of flavones and flavanones from 2′-hydroxydihydrochalcones as common intermediates, depending on oxidants and additives, via discriminate oxidative cyclization sequences involving dehydrogenation, respectively, in a highly atom-economic manner.

Divergent and versatile synthetic routes to flavones and flavanones via efficient Pd(ii) catalysis are disclosed.

Flavones and flavanones are widely occurring natural flavonoids produced by various medicinal plants and their synthetic derivatives, featuring a main 15-carbon skeleton possessing 2 phenyl rings and 1 oxacycle.¹ In recent decades, they have been considered privileged structures exhibiting various biological activities,² such as anti-inflammatory,³ anti-cancer,⁴ neuroprotective,⁵ and estrogen-related functions⁶ (Fig. 1). As routes towards such privileged flavonoids, many strategies, including the Allan–Robinson reaction for flavones and intramolecular conjugate addition of 2′-hydroxychalcones for flavanones, have been reported.⁷ Among these, intramolecular cyclization of 2′-hydroxychalcone intermediates was conventionally used for the synthesis of flavanones due to the readily available properties of the substrates through the condensation of 2′-hydroxy-acetophenones and corresponding aldehydes.⁸ In addition, such flavanones can be readily converted into flavones via further oxidation processes (Scheme 1).⁹ Thus, these types of flavonoid synthesis involving intramolecular conjugate addition have been generally used for flavonoid synthesis,¹⁰ but they generally have drawbacks of requiring harsh conditions such as acidic or basic reflux conditions for cyclization, indicating that chemically labile compounds may in some cases not be tolerable in reaction conditions.¹¹ Additional oxidation steps in which flavanones are transformed into flavones often require the use of strong oxidants such as I₂ that enable side reactions to occur.¹² In this regard, novel synthetic routes featuring transformative and compatible reaction conditions toward flavonoids have been pursued in recent decades. In particular, given the increasing importance of constructing a privileged chemical library for probing biological systems, efficient and divergent synthesis of flavonoids is necessary.¹³Open in a separate windowFig. 1Examples of bioactive flavonoids.Open in a separate windowScheme 1Synthetic strategy for flavonoids pursued in this study.Taken together, it is important to develop a novel and versatile synthetic transformation of common substrates into flavones and flavanones under mild conditions and such a transformation is also expected to enable straightforward reactions for the construction of a privileged flavonoid library. As mentioned above, 2′-hydroxychalcones have been conventionally used as main precursors in flavonoid synthesis, but they are reactive and unmanageable in some cases due to their reactive α,β-unsaturated carbonyl and enol ether moieties. In addition, their use is generally involved with several disadvantages, as mentioned above.¹⁴ Thus, we think that the use of common intermediates instead of 2′-hydroxychalcones that is traditionally used but somewhat problematic is required. Recently, direct β-functionalization of simple ketones via several catalysts using transition metals and light was reported,¹⁵ indicating that simple ketones can be useful and potential surrogates of α,β-unsaturated ketones for further oxidative catalysis. In addition, we reported that chromanones, simple ketones, can be converted into flavones and flavanones via palladium(ii)-catalyzed dehydrogenation-mediated coupling sequences with arylboronic esters and acids, respectively, and also recently reported that N-substituted azaflavanone can be synthesized from N-substituted aminodihydrochalcones via Pd(ii)-catalyzed oxidative cyclization.¹⁶ Inspired by these previous works, we sought to find novel and divergent synthetic routes to a variety of privileged flavonoids, particularly flavones and flavanones using common starting materials.Herein, we report palladium(ii)-catalyzed oxidative cyclization of 2′-hydroxydihydroxychalcones that are novel and tolerable isosteres of 2′-hydroxychalcones as an efficient and divergent route for the synthesis of flavones and flavanones. To find an optimal reaction condition where flavone and flavanone were synthesized via Pd(ii)-catalyzed oxidative cyclization from the common intermediate in independent manners, simple 2′-hydroxydihydrochalcone was selected as the model compound to screen the reaction conditions (ii)-catalyzed dehydrogenation to occur with Pd(TFA)₂ and DMSO under an O₂ atmosphere, which is eco-friendly oxidant.17 The use of this reaction condition resulted in the formation of flavanone 4a as the major product (31% yield, entry 1) and flavone 3a with 12% yield, along with a small amount of 2′-hydroxychalcone 2a (14%). This result implied that 2′-hydroxydihydrochalcone could be dehydrogenated and slightly transformed into desired flavonoids under the reaction conditions featuring Pd(ii) catalysis. Based on the results, we tried to optimize the reaction conditions by using additives such as heterocyclic amines or inorganic bases as Pd(ii) ligands. In the presence of most of the heterocyclic amines and K₂CO₃, the overall yields of the reactions for the synthesis of flavonoids were significantly increased (entries 2–5). Interestingly, the catalytic system featuring 2,2′-bipyridine (bpy) as a ligand provided flavone 3a in 55% yield as a major product, along with flavanone 4a in 10% yield, indicating that bidentate amine was better than the other monodentate amines, including pyridine as a Pd(ii) ligand, under incorporating conditions (entry 6). Notably, the use of 5-nitro-1,10-phenanthroline as a ligand enables the reaction to exclusively yield flavone 3a with the highest yield of 81% and flavanone 4a in 2% yield (entry 7).Optimization of the reaction conditions^a