Central Ring Research Articles

Crystal structures of six complexes of phosphane chalcogenides R 1 R 2 R 3PE (R = tert-butyl or isopropyl, E = S or Se) with the metal halides MX 2 (M = Pd or Pt, X = Cl or Br), two halochalcogenylphosphonium derivatives ( t Bu2 iPrPEBr)2[Pd2Br6] and one hydrolysis product

The L 2 MX 2 complexes 1–5 (1: L = t BuiPr2PSe, M = Pd, X = Cl; 2: L = t Bu2 iPrPSe, M = Pd, X = Cl; 3: L = t Bu2 iPrPSe, M = Pd, X = Br; 4: L = t Bu2 iPrPS, M = Pd, X = Br; 5: L = t Bu2 iPrPS, M = Pt, X = Cl) {systematic names: (tert-butyldiisopropylphosphine selenide-κSe)dichloridopalladium(II), [PdCl2(C10H23PSe)2] (1), (di-tert-butylisopropylphosphine selenide-κSe)dichloridopalladium(II), [PdCl2(C11H25PSe)2] (2), dibromido(di-tert-butylisopropylphosphine selenide-κSe)palladium(II), [PdBr2(C11H25PSe)2] (3), dibromido(di-tert-butylisopropylphosphine sulfide-κS)palladium(II), [PdBr2(C11H25PS)2] (4), dichlorido(di-tert-butylisopropylphosphine sulfide-κS)palladium(II), [PdCl2(C11H25PS)2] (5)} all display a trans configuration with square-planar geometry at the metal atom. Compounds 2 and 3 are isotypic. The molecules of 1 and 4 display crystallographic inversion symmetry; compound 5 involves two independent molecules, each with inversion symmetry but with differing orientations of the trialkylphosphane groups. Chemically equivalent bond lengths all lie in narrow ranges, whereby the values for palladium and platinum compounds scarcely differ. Compound 6, ( t BuiPr2PS)2Pd2Cl4 {systematic name: di-μ-chlorido-bis[(tert-butyldiisopropylphosphine sulfide-κS)chloridopalladium(II)], [PdCl2(C10H23PS)2]}, is dinuclear with a central Pd2Cl2 ring, and displays crystallographic inversion symmetry. The bonds to the bridging are longer than those to the terminal chlorine atoms; the Pd—S bond is shorter than the M—S bonds in 4 and 5, reflecting the weaker trans influence of (bridging) chlorine compared to sulfur. Compounds 7 and 8, 2( t Bu2 iPrPEBr)+ [Pd2Br6]2− with E = S for 7 and Se for 8 {systematic names: (bromosulfanyl)di-tert-butylisopropylphosphanium di-μ-bromido-bis[dibromidopalladium(II)], (C11H25BrPS)2[Pd2Br6] (7) and (bromoselanyl)di-tert-butylisopropylphosphanium di-μ-bromido-bis[dibromidopalladium(II)], (C11H25BrPS2)2[Pd2Br6], (8)}, were obtained by oxidizing the appropriate PdII precursors with elemental bromine; they are not isotypic. The ions are connected by very short halogen bonds Br...Br. For both compounds, two E...Br contacts further link the cations and anions to form ribbons. Compound 9 {systematic name: bis[dimethyl(sulfanylidene)phosphinito-κSe]bis(hydroxydiisopropylphosphine selenide-κSe)palladium(II), [Pd(C6H14OP)2(C6H15OP)2], {(iPr2PSeO)2H}2Pd, is a hydrolysis product with inversion symmetry and contains an intramolecular P—O...H—O—P group with a disordered hydrogen atom. Compounds 1–6 and 9 show few, if any, short intermolecular contacts, although some H...M contacts are observed. A problem with atom-type assignment for structure refinement is discussed.

Mapping the Active Galactic Nucleus Effects on the Stellar and Gas Properties of NGC 5806

Abstract It is commonly accepted that active galactic nuclei (AGNs) have a strong impact upon the evolution of their host galaxies, but the processes by which they do so are not fully understood. We aim to further the understanding of AGN feeding and feedback by examining an active galaxy using spatially resolved spectroscopy. We analyze integral field spectroscopy of the active galaxy NGC 5806, obtained using the Very Large Telescope Multi-Unit Spectroscopic Explorer. We map the dynamics of gas and stars, as well as gas optical emission line fluxes throughout the central 8 × 8 kpc2 of the galaxy. We use emission line ratios to map gas metallicity and identify regions of gas excitation dominated by AGN/shocks or star formation. We also determine the average stellar population age and metallicity, and model the rotation and dynamics of the galaxy. We find that NGC 5806 has a star-forming circumnuclear ring, with a projected radius of ~400 pc. The dynamics of this galaxy are driven by a large-scale bar, which transports gas from the spiral arm to the central ring and potentially fuels the AGN. We also observe AGN-dominated gas excitation up to 3.3 kpc away from the center of the galaxy, showing the extended AGN effect on the gas in the central regions of the galaxy.

Dual step-index ring core antiresonant fiber for broadband transmission of numerous OAM modes with high purity and quality

We present a design strategy of a dual step-index ring core antiresonant fiber (DSI-RC-ARF) to significantly enhance the number of orbital angular momentum (OAM) modes while preserving their high purity and transmission quality over the O-E-S-C-L-U bands. The proposed fiber features a central ring of high refractive index, surrounded by outer and inner rings of refractive indices that gradually decrease from the central ring in both directions. The proposed fiber consists of a unique core arrangement having a central ring with a higher refractive index that can support up to 206 OAM modes across the 1.28 μm to 1.70 μm wavelength range without any higher-order radial modes or phase distortion. Additionally, the core is surrounded by inner and outer rings with gradually varying refractive indices, which helps to maintain the mode quality above 97% and mode purity mostly above 98%. The fiber also renders a uniform dispersion variation with wavelength, large effective mode area, nonlinear coefficients below 1.62 /W/km throughout the entire bandwidth, very low confinement loss ranging from 10−11 to 10−9 dB/m, and longer 2π and 10 ps walk-off length for higher-order OAM modes with ellipticity and bending. This innovative fiber design enhances the capabilities of antiresonant fibers in modern communication systems, making it ideal for efficient broadband transmission of high-capacity OAM modes.

Tale of Three Dithienylethenes: Following the Photocycloreversion with Ultrafast Spectroscopy and Quantum Dynamics Simulations.

Photocycloreversion reactions of three diarylethene derivatives whose structures differ only in the placement of two sulfur atoms in the cyclopentene rings are investigated. Despite the minuscule differences between the molecules, both the yields and times of the photoreactions vary considerably. Using UV-vis and infrared femtosecond spectroscopy and quantum chemical dynamics simulations, we elucidate the relationships among the quantum yield, electronic and vibrational relaxation time, and structural properties of the dithienylethene photoswitches. We show that the local aromaticity of the molecule's central ring could be one of the predictors of the quantum yield and the rate of cycloreversion. While from the perspective of electronic dynamics, the cycloreversion is completed within a few picoseconds at most, all three derivatives exhibit much longer (10-25 ps) nuclear rearrangement times that determine the actual times of stable photoproduct formation.

Compensating the Meniscus Effect in Phase Contrast Microscopy Using an LCD for Adaptive Condenser Annulus Shifting.

The meniscus effect in cell culture vessels limits the observable areas with phase contrast microscopy. For meniscus effect compensation in microtiter plates (MTPs), we present a method using an LCD to replace the fixed condenser annulus, which enables adaptive annulus shifting based on image analysis. This approach led to an increase in phase contrast area by a factor of 8.3. Utilizing a standard phase contrast microscope, we substituted the static condenser annulus with a transparent LCD that displays an adaptive annulus, which can be repositioned to counteract meniscus-induced refraction across an entire MTP-24 well. We developed image analysis using Bertrand lens images to determine the misalignment between annulus center and phase ring, enabling the calculation of the required annulus shift. Experiments demonstrate the effectiveness of this image analysis technique. The detected shift was translated into new LCD settings through a linear regression model to ensure proper alignment for the following image. We proved that an algorithm based on background brightness yields a reliable metric for assessing phase contrast conditions within well-plates. The proposed approach substantially increased the phase contrast area in 24-well MTPs at 10× magnification from 5.0% with conventional microscopy to 41.9%, thereby restoring phase contrast conditions throughout the well, except near the edges.

Stabilizing Contorted Doubly-Reduced Tetraphenylene with Heavy Alkali Metal Complexation: Crystallographic and Theoretical Evidence.

The two-fold reduction of tetrabenzo[a,c,e,g]cyclooctatetraene (TBCOT, or tetraphenylene, 1) with K, Rb, and Cs metals reveals a distinctive core transformation pathway: a newly formed C-C bond converts the central eight-membered ring into a twisted core with two fused five-membered rings. This C-C bond of 1.589(3)-1.606(6) Å falls into a single σ-bond range and generates two perpendicular π-surfaces with dihedral angles of 110.3(9)°-117.4(1)° in the 1TR 2- dianions. As a result, the highly contorted 1TR 2- ligand exhibits a "butterfly" shape and could provide different coordination sites for metal-ion binding. The K-induced reduction of 1 in THF affords a polymeric product with low solubility, namely [{K+(THF)}2(1TR 2-)] (K2-1TR 2-). The use of a secondary ligand facilitates the isolation of discrete complexes with heavy alkali metals, [Rb+(18-crown-6)]2[1TR 2-] (Rb2-1TR 2-) and [Cs+(18-crown-6)]2[1TR 2-] (Cs2-1TR 2-). Both internal and external coordination are observed in K2-1TR 2-, while the bulky 18-crown-6 ligand only allows external metal binding in Rb2-1TR 2- and Cs2-1TR 2-. The reversibility of the two-fold reduction and bond rearrangement is demonstrated by NMR spectroscopy. Computational analysis shows that the heavier alkali metals enable effective charge transfer from the 1TR 2-TBCOT dianion, however, the aromaticity of the polycyclic ligand remains largely unaffected.

High-Pressure Polymerization of Phenol toward Degree-4 Carbon Nanothread.

Saturated sp3-carbon nanothreads (CNTh) have garnered significant interest due to their predicted high Young's modulus and thermal conductivity. While the incorporation of heteroatoms into the central ring has been shown to influence the formation of CNTh and yield chemically homogeneous products, the impact of pendant groups on the polymerization process remains underexplored. In this study, we investigate the pressure-induced polymerization of phenol, revealing two phase transitions occurring below 0.5 and 4 GPa. Above 20 GPa, phenol polymerizes into degree-4 CNThs featuring hydroxyl and carbonyl groups. Hydrogen transfer of hydroxyl groups was found to hinder the formation of degree-6 nanothreads. Our findings highlight the crucial role of the hydroxyl group in halting further intracolumn polymerization and offer valuable insights for future mechanism research and nanomaterial synthesis.

Polarization-insensitive, negative indexed inverted U-shaped flexible metamaterial absorber based on microstructure resonator for multi-band energy harvesting

This article presents a polarization-insensitive, negative indexed inverted U-shaped flexible metamaterial absorber based on a microstructure resonator for multi-band energy harvester application. The vertical inverted U-shaped joint and central split ring resonator together create significant resonance covering three consecutive L-, S-, and C-band absorption peaks for four resonance frequencies: 1.975 GHz with 99.99% absorption, 2.85 GHz with 99.28% absorption, 5.265 GHz with 96.79% absorption, and 5.5 GHz with 89.12% absorption. The design has a rare double negative metamaterial feature at 5.265 GHz, while a balanced geometrical appearance that is polarization insensitive for θ and φ improved the structure’s durability and tunability. Finite computer simulation technology was used to simulate and examine the mechanisms involved in absorption at 1— 6 GHz. Based on Rogers RO4350 B and copper, the structural design showed excellent absorption for 15° and 30° bends and 2 × 4, 4 × 8 arrays with an efficiency of 96.38% at an incidence angle of 30° in transverse magnetic mode, a 3x 3 array was developed for energy harvesting. For energy harvesting applications using array structure, the efficiency parameter is unnoted in most of the reported articles. Moreover, the array demonstrated polarization insensitivity for both transverse electric and transverse magnetic modes at angles of 0°, 30°, and 60°. The proposed quad-band absorber shows significant potential for energy harvesting applications.

Recent Achievements in the Synthesis of Carbazole Derivatives

Abstract: Carbazole derivatives possess tricyclic structure consisting of two benzene rings fused on both sides with the central pyrrole ring. These compounds diversely appear both in natural and synthetic sources. Carbazole-based compounds have a wide range of bioactivities such as antimicrobial, anticancer, antiparasitic, antihypertensive, antineuropathic, and anti-inflammatory activities. Some carbazole derivatives have been employed as drugs in the market. The synthesis of carbazole derivatives has attracted intensive interest from chemists and a huge number of studies on the synthesis of carbazole-based compounds have been published over the years. In this article, we will give a comprehensive review of studies on the synthesis of carbazoles, which date back to 2012. One hundred twenty-six studies on the synthesis of carbazoles are summarized. A huge number of novel methods have been developed to improve efficiency or employ environmentally benign procedures. In most cases, reaction mechanisms were included. The review article might be useful for chemists who work in the synthesis of heterocycles or drug chemistry.

Multifocal electroretinogram evaluation of different optical coherence tomography patterns of diabetic macular edema

Purpose To correlate macular function to morphological patterns of diabetic macular edema (DME) observed by optical coherence tomography (OCT). Patients and methods This study included 100 DME eyes and 60 control eyes. OCT patterns of DME were divided into: Type 1: diffuse retinal thickening (DRT); Type 2: cystoid macular edema (CME); Type 3: neurosensory detachment (NSD); and Type 4: the combined type that was further subdivided into: Type 4a: DRT with CME, Type 4b: DRT with NSD, and Type 4c: CME with NSD. These types were correlated with LogMAR VA and P1 wave amplitude and implicit time of multifocal electroretinogram. Results In both central ring 1 and paracentral ring 2, P1 amplitude was significantly reduced in all types of DME compared with control group. P1 amplitude was highest in Type 1, and lowest in Type 4c compared with other DME types. P1 implicit time was significantly delayed in all types, and significantly delayed in Type 4c compared with Type 1. Conclusion DRT was the best type for macular function, CME was associated with decreased P1 wave amplitude in central macular ring, NSD was associated with decreased P1 wave amplitude in the paracentral macular ring, combined CME with NSD carried the poorest visual function. From a practical point of view, combining OCT and multifocal electroretinogram testing may offer a potent method to assess the degree of retinal injury.

Crystal structure of p-xylene@silicalite-1.

The crystal structure of a highly loaded complex of silicalite-1 (SL-1) with eight mol-ecules of p-xylene per unit cell has been solved by single-crystal X-ray diffraction. In the crystal, four symmetrical Si24O48·2C8H10 subunits per unit cell are observed. The p-xylene mol-ecules sit at two different positions within the SL-1 channels. The first mol-ecule is located at the inter-section of the sinusoidal and straight channels, while the second guest mol-ecule is positioned in the center of the double ten-membered ring (10-MR) of the sinusoidal channel.

Heptene End-capped Thiele Hydrocarbons with Tunable Configuration and Emission and On-surface Transformation via Annulation

We report a para-quinodimethane skeleton (p-QDM)-based polycyclic aromatic hydrocarbon (PAH) with heptenes as end-capping groups and F-substitutents in the central six-membered ring. This compound shows the syn-configuration in one crystal...

Annulated carbocyclic gallylene and bis-gallylene with two-coordinated Ga(i) atoms.

The first carbocyclic gallylene [(ADC)2Ga(GaI2)] and bis-gallylene [(ADC)Ga]2 (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3) featuring a central C4Ga2 ring annulated between two 1,3-imidazole rings are prepared by KC8 reductions of [(ADC)GaI2]2. Treatment of [(ADC)Ga]2 with Fe2(CO)9 affords complex [(ADC)GaFe(CO)4]2 in which each Ga(i) atom serves as a two-electron donor. [(ADC)Ga]2 activates white phosphorus (P4) and the Csp2 -F bond of aryl fluorides (ArF) to yield compounds [(ADC)Ga(P4)]2 and cis-/trans-[(ADC)GaF(Ar)]2, respectively. [(ADC)Ga]2 undergoes oxidation with (Me2S)AuCl to give [(ADC)GaCl2]2, while with PhN[double bond, length as m-dash]NPh it forms [1 + 4]-cycloaddition product [(ADC)GaN(Ph)N[double bond, length as m-dash]C6H5]2 by the dearomatization of one of the phenyl rings.

Enhancing optoelectronic performance of organic solar cells: Alkoxy substitution of central cores and π-bridge units in fully non-fused ring electron acceptors

To systematically elucidate the impact of fluorination and alkoxy modification on the fully non-fused ring electron acceptors (NFREAs) for organic solar cells (OSCs), six fully NFREAs were engineered featuring a benzene core, a selenophene-thiophene unit as the π-bridge, and IC-2F end groups. The derivatives R-D2F and R-D2O were designed by introducing para-substituted fluorine and alkoxy groups onto the central benzene ring of R. Further modifications to the π-bridge of R-D2O, involving variations in the position and number of alkoxy groups, resulted in the derivatives R-DW4O, R-DN4O, and R-D6O. Molecular Dynamics (MD), Density Functional Theory (DFT), and Time-Dependent Density Functional Theory (TD-DFT) simulations were used to predict the optoelectronic properties of these compounds. A comprehensive analysis was conducted on aspects including intramolecular non-covalent interactions, transition density matrix (TDM), electron-hole distributions, charge density difference (CDD), and inter-fragment charge transfer (IFCT). Additionally, the electron transfer rate constants (Ke) and electron mobility (μe) of dimeric structures were calculated to better understand the electronic transmission behavior of these acceptor molecules. The results show that alkoxy substitution on the central core, rather than fluorine substitution, enhances planarity, strengthens intermolecular interactions, reduces the energy gap, induces a red shift in the absorption spectrum, and improves electron excitation efficiency and net charge transfer. The addition of alkoxy groups to the π-bridge further promotes non-covalent interactions, enhancing light absorption and increasing light harvesting efficiency (LHE). Among the derivatives, R-D6O, which features cooperative alkoxy substitution on both the thiophene and selenophene units, exhibits the highest electron mobility, making it a promising candidate for OSC applications. These findings provide valuable insights into the design of high-performance fully NFREAs for OSCs.

Structure-activity relationship expansion and microsomal stability assessment of the 2-morpholinobenzoic acid scaffold as antiproliferative phosphatidylcholine-specific phospholipase C inhibitors.

Dysregulation of choline phospholipid metabolism and overexpression of phosphatidylcholine-specific phospholipase C (PC-PLC) is implicated in various cancers. Current known enzyme inhibitors include compounds based on a 2-morpholino-5-N-benzylamino benzoic acid, or hydroxamic acid, scaffold. In this work, 81 compounds were made by modifying this core structure to explore the pharmacophore. Specifically, these novel compounds result from changes to the central ring substitution pattern, alkyl heterocycle and methylation of the N-benzyl bridge. The anti-proliferative activity of the synthesised compounds was assessed against cancer cell lines MDA-MB-231 and HCT116. PC-PLCBC enzyme inhibition was also assessed, and the development of a pharmacokinetic profile was initiated using a microsomal stability assay. The findings confirmed the optimal pharmacophore as a 2-morpholino-5-N-benzylamino benzoic acid, or acid derivative, scaffold, and that this family of molecules demonstrate a high degree of stability following treatment with rat microsomes. Additionally, benzylic N-methylated compounds were the most biologically active compounds, encouraging further investigation into this region of the pharmacophore.

Quantum-Classical Simulations Reveal the Photoisomerization Mechanism of a Prototypical First-Generation Molecular Motor.

Light-driven molecular rotary motors convert the energy of absorbed light into unidirectional rotational motion and are key components in the design of molecular machines. The archetypal class of light-driven rotary motors is chiral overcrowded alkenes, where the rotational movement is achieved through consecutive cis-trans photoisomerization reactions and thermal helix inversion steps. While the thermal steps have been rather well understood by now, our understanding of the photoisomerization reactions of overcrowded alkene-based motors still misses key points that would explain the striking differences in operation efficiency of the known systems. Here, we employ quantum-chemical calculations and nonadiabatic molecular dynamics simulations to investigate the excited-state decay and photoisomerization mechanism in a prototypical alkene-based first-generation rotary motor. We show that the initially excited bright state undergoes an ultrafast relaxation to multiple excited-state minima separated by low energy barriers and reveal a slow picosecond-timescale decay to the ground state, which only occurs from a largely twisted dark excited-state minimum, far from any conical-intersection point. Additionally, we attribute the origin of the high yields of forward photoisomerization in our investigated motor to the favorable topography of the ground-state potential energy surface, which is controlled by the conformation of the central cyclopentene rings.

Relationship Between Electronegativity of the Extra-Framework Cations and Adsorption Capacity for CO2 Gas on Mordenite Framework.

Synthetic mordenite is widely used as a molecular sieve, adsorbent, and catalyst. To enhance these functionalities, it is crucial to understand the ion-exchange properties and cation-exchange sites of the zeolite. In this study, we analyzed the structural changes in fully Cs-, Sr-, Cd-, and Pb-exchanged mordenite by using synchrotron X-ray powder diffraction under ambient conditions. Rietveld structure refinement revealed that the Cs+ cation is predominantly located near the 8-membered ring (8MR) due to its low electronegativity and hydration energy. In contrast, divalent cations such as Sr2+ and Cd2+ cations, with higher hydration energies compared to monovalent cations, are present as hydrated ions at the center of the 12-membered ring along the c-axis (12MRc). Pb2+ ions, due to their higher electronegativity than the framework atoms, exhibit a strong affinity for the electron cloud of framework oxygen atoms, which positions them close to the wall of the 12MRc. The observed differences in the locations of the extra-framework cations are attributed to electrostatic and hydration effects. Furthermore, the CO2 adsorption capacity was assessed based on the type and site of exchangeable cations. The findings indicate that an increase in the CO2 adsorption capacity correlates with the number of cations that can effectively interact with CO2.

Total Syntheses of Scabrolide B, Ineleganolide, and Related Norcembranoids.

Concise total syntheses of several 5/7/6 norcembranoids, including ineleganolide, scabrolide B, sinuscalide C, and fragilolide A have been achieved through a fragment coupling/ring closure approach. The central seven-membered ring was forged through sequential Mukaiyama-Michael/aldol reactions using norcarvone and a decorated bicyclic lactone incorporating a latent electrophile. Subsequent manipulations installed the reactive enedione motif and delivered scabrolide B in 11 steps from a chiral pool-derived enone. Finally, ineleganolide, sinuscalide C, and fragilolide A were each accessed in one additional step.

A Stable Carbon-Centered Radical Showing Six Amphoteric Redox States.

An air- and moisture-stable hydrocarbon radical with four six- and three five-membered rings alternately fused to a heptacycle was obtained by ortho fusion in a suitably ortho,ortho'-substituted diphenylfluorene and subsequent re-establishment of the conjugation. The radical was obtained in five consecutive steps from commercially available starting materials with a total yield of 34 %; key steps are Suzuki couplings and cyclizing SEAr reactions. Mesityl substituents at the five-membered rings ensure the stability of the radical. This cyclopenta-fused polyaromatic hydrocarbon (CP-PAH) was characterized by EPR and UV/Vis spectroscopy and by cyclic voltammetry. Quantum chemical calculation disclosed further properties and led to simulated spectra (spin densities, aromaticity, orbital energies, and UV/Vis/NIR). This radical is best described with the unpaired electron centered in the outer five-membered rings; these resonance formulas show the largest number of fully intact benzene rings. Its triradical character was computed to be very small and can be neglected. The five-membered rings show notable antiaromatic character, especially in the central ring. The constitution of the radical could be further substantiated by X-ray crystallographic analysis of its direct precursor.

Structural studies of (2R,3R)-(+)-bis(diphenylphosphino)butane and (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl

Abstract The crystal structures of two chiral phosphanes, ((R,R)-chiraphos = (2R,3R)-(+)-2,3-bis(diphenylphosphino)butane and R-Tol-BINAP = (R)-(+)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl) are unambiguously determined by X-ray crystallography and reported for the first time. The aim is to understand the structural characteristics and their chiral arrangement of the molecules. The (R,R)-chiraphos structure was solved in the orthorhombic space group P212121 while R-Tol-BINAP was solved in the triclinic space group P1. This set of compounds demonstrates attractive intramolecular phenyl ring interactions involving two terminal phenyl rings in (R,R)-chiraphos, while a terminal tolyl ring and the central binaphthyl ring occurs in R-Tol-BINAP. The crystal structure analyses also revealed that all aromatic units have close C–H⋯arylcentroid weak contacts forming continuous networks of columns and layers in (R,R)-chiraphos and R-Tol-BINAP respectively.