Active Precatalysts Research Articles

Pd(0)/Xantphos-Catalyzed Benzylic C(sp3)-O Arylation of Benzyl Heteroaryl Ethers: Reduction of Pd(II) to Pd(0) by Xantphos.

Herein, we report the synthesis of 1,1-diarylmethanes via palladium-catalyzed benzylic C(sp3)-O arylation of benzyl alcohol derivatives. An efficient, straightforward approach to synthesizing Pd(0)(xantphos)2 was developed through in situ reduction of Pd(II) to Pd(0) with the bidentate tertiary phosphine xantphos, which proved to be a highly active precatalyst in the Suzuki-Miyaura cross-coupling reaction of benzyl heteroaryl ethers.

Hydroboration of Terminal Alkynes Catalyzed by a Mn(I) Alkyl PCP Pincer Complex Following Two Diverging Pathways.

A stereo- and regioselective Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The hydroboration reaction is highly Z-selective in the case of aryl alkynes and E-selective in the case of aliphatic alkynes. The reaction requires no additives or solvents and proceeds with a catalyst loading of 1 mol % at 50-70 °C. The most active precatalyst is the bench-stable alkyl Mn(I) complex cis-[Mn(PCP-iPr)(CO)2(CH2CH2CH3)]. The catalytic process is initiated by the migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate. This species undergoes C-H and B-H bond cleavage of the alkyne (aromatic alkynes) and HBPin (in the case of aliphatic alkynes) forming the active Mn(I) alkynyl and boryl catalysts [Mn(PCP-iPr)(CO)(C≡CR)] and [Mn(PCP-iPr)(CO)(BPin)], respectively. A broad variety of aromatic and aliphatic alkynes was efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations. The functionalized alkenes can be used for further applications in cross-coupling reactions.

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach.

The utilization of biobased feedstocks to prepare useful compounds is a pivotal trend in current chemical research. Among a varied portfolio of naturally available starting materials, fatty acids are abundant, versatile substrates with multiple applications. In this context, the ethenolysis of unsaturated fatty acid esters such as methyl oleate is an atom-economical way to prepare functional C10 olefins with a biobased footprint. Despite the existence of a variety of metathesis catalysts for the latter process, there is a lack of readily available, efficient, and inexpensive catalytic systems based on earth-abundant metals (Mo, W) whose preparation does not require sophisticated syntheses and manipulations. Here, a systematic exploration of homogeneous and heterogeneous inorganic Mo, W (oxy)halides shows that MoOCl4, while inactive as a homogeneous species, forms active and selective silica-supported ethenolysis precatalysts able to reach equilibrium conversion of methyl oleate within a few minutes upon activation with SnMe4. Such heterogeneous MoOCl4-based precatalysts were easily accessed through mechanochemical solvent-free procedures and found to contain, upon characterization by elemental analysis and Raman spectroscopy, isolated (≡SiO)Mo(=O)Cl3 units or polymeric silica-supported [-O(≡SiO)nMoCl4-nO-]m (n = 1, 2) complexes depending on the molybdenum loading. The former isolated species exhibited a higher catalytic performance. The developed heterogeneous precatalysts could be applied to the ethenolysis of various substrates, including polyunsaturated fatty acid esters and industrial fatty acid methyl ester (FAME) mixtures from palm oil transesterification.

Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)‐Catalyzed Hydroaminations and Hydrohydrazinations

Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing to their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, a series of ferrocenyl diphosphines functionalized with no, one or two ylide moieties and their corresponding bimetallic gold complexes were prepared. The complexes feature an anti‐conformation of the two phosphine moieties, guaranteeing the presence of two independent metal centers. Comparative studies of the complexes in the hydroamination and hydrohydrazination of alkynes revealed a significant increase in catalytic activity for each newly introduced ylide group. The di‐YPhos ligands were revealed to be the most active precatalysts, functioning effectively even at 0.1 or 0.2 mol% catalyst loading. This catalytic efficiency was demonstrated for a series of alkynes, amines and hydrazines.

Synthesis and Characterization of Dearomatized Pyridine‐Derived Alkyl‐Amido‐tert‐Butylphosphine Iron(II) Complexes

AbstractNeutral three‐coordinate iron alkylidenes of the form PN−Fe=CHR have been proposed as viable candidates for alkene metathesis. Indeed, during the final stages of preparing this current study, a separate report disclosed that dearomatized PN−Fe‐alkyl complexes are active precatalysts for ring‐opening metathesis polymerization (ROMP) of norbornene implicating PN−Fe=CHR species as possible intermediates. In yet another separate report, we prepared Zn analogues of PN−Fe‐alkyl complexes and herein provide an account for the synthesis, characterization, and reactivity of some new iron complexes with the same tBu substituted PN platform.

Ligand-Enabled Copper-Mediated Radioiodination of Arenes.

The discovery of a copper precatalyst that facilitates the key mechanistic steps of arene halodeboronation has allowed a step change in the synthesis of radioiodine-containing arenes. The active precatalyst [Cu(OAc)(phen)2]OAc was shown to perform room temperature radio-iododeboronation of aryl boronic acids with 1-2 mol % loadings and 10 min reaction times. These mild conditions enable particularly clean reactions, as demonstrated with the efficient preparation of the radiopharmaceutical and SPECT tracer, meta-iodobenzylguanidine (MIBG).

Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine.

There are few literature reports on using precatalysts based on ruthenium(II/III) ions in the polymerization of olefins. Therefore, a new coordination compound was designed based on ruthenium(III) ion and 2-phenylpyridine. The resulting monocrystal was characterized by X-ray diffraction (XRD), solid-state (photo)IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The new ruthenium(III) complex compound was used as a precatalyst in the oligomerization reactions of ethylene, 2-propen-1-ol, 2-chloro-2-propen-1-ol, 3-butene-2-ol and 2,3-dibromo-2-propen-1-ol with methylaluminoxane and ethylaluminium dichloride as activators. The catalytic activity of the newly discovered ruthenium(III) complex compound ranges from 159.5 (for 2-chloro-2-propen-1-ol) to 755.6 (for ethylene) g mmol-1 h-1 bar-1, indicating that it is a chemical compound with high catalytic activity. In addition, the oligomerization reaction products were subjected to physicochemical characterization, using BET (Brunauer-Emmett-Teller isotherm), mass spectrometry (MALDI-TOF-MS), Fourier transform infrared (FT-IR) spectroscopy, NMR, TGA, differential scanning calorimetry (DSC), and the morphology of the porous polymeric materials was investigated by SEM. The distinguishing feature of the obtained precatalyst is its high catalytic activity under mild reaction conditions, a rare phenomenon. Compared with other precatalysts, it is the most active ruthenium(II/III) ion-based catalytic material used in oligo- and polymerization reactions of ethylene.

Magnesium(ii) complexes supported by indole- and pyrrole-containing Schiff-base ligands: syntheses, structures, and applications as precatalysts in the hydroboration of nitriles and alkynes

Five magnesium compounds were synthesized. They are active precatalysts for the hydroboration of nitriles and alkynes. The catalytic reactions feature mild reaction conditions, excellent functional group tolerance, and high yields.

Group I Alkoxides and Amylates as Highly Efficient Silicon-Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes.

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KOt Amyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3 SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition-metal catalysts for this transformation. Preliminary evidence suggests the formation of hypercoordinated intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si-N bond formation.

Silica-magnesium-titanium Ziegler-Natta catalysts. Part 1: Structure of the pre-catalyst at a molecular level

In this paper, which is the first part of a more extended work, we elucidate the molecular level structure of a highly active SiO2-supported Ziegler-Natta precatalyst obtained by reacting a dehydroxylated silica and a solution of an organomagnesium compound with TiCl4. The synergetic combination of Ti K-edge and Ti L3-edge X-ray Absorption spectroscopy (XAS) and diffuse reflectance UV–Vis spectroscopies, complemented by Density Functional Theory (DFT) simulations, indicate that small TiCl3 clusters similar to β-TiCl3 coexist with isolated monomeric Ti(IV) species. Ti K-edge Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy allows the quantification of these two phases and demonstrates that the Ti(IV) sites are 6-fold coordinated (either by six chlorine ligands or by five chlorine and one oxygen ligands), but highly distorted, similar to what is modelled for TiCl4-capped MgCl2 nanoplatelets. Finally, IR spectroscopy suggests that the MgCl2 phase has a molecular character (Far-IR) and that the only accessible Mg2+ sites are uncoordinated cations acting as Lewis acid sites (IR of CO adsorbed at 100 K). Based on these experimental findings, we propose the co-existence in the precatalyst of small TiCl3 clusters and of mixed oxo-chloride magnesium-titanium structures deposited at the silica surface. The evolution of the precatalyst in the presence of the activator and of the monomer is discussed in the second part of this work.

Heterocene Catalysts and Reaction Temperature Gradient in Dec-1-ene Oligomerization for the Production of Low Viscosity PAO Base Stocks

Hydrogenated oligomers of higher α-olefins (primarily, dec-1-ene) with uniform structure represent high-quality poly-α-olefin oil (PAO) base stocks. High yields of lightweight dec-1-ene oligomers (DPn = 3–4) can be achieved by using 5,10-dihydroindeno[1,2-b]indole-based zirconium ansa-complexes, “heterocenes”. Unusual catalytic behavior of heterocenes served as a starting point for the present study, during which new, more synthetically available and active heterocene precatalysts were synthesized, and a novel oligomerization method, based on a reaction temperature gradient, was developed. A gradual decrease of the oligomerization temperature as dec-1-ene was consumed resulted in decreased dimer formation (down to 10%) and increased oligomer yields (up to 84%). After hydrogenation, low- and medium-viscosity PAO base oils with uniform structure and high viscosity indexes were obtained.

Structural Evolution and Durability of Ultrafine NiFe Phosphide Nanoparticle/Carbon Composite Films in Water Oxidation at High Current Densities

NiFe phosphide (NiFe-P) is a highly active precatalyst for the oxygen evolution reaction (OER), but its compositional and structural changes during sustained electrolysis have not been thoroughly understood. Moreover, the size control of NiFe-P particles remains challenging yet desirable without multistep synthesis or surface capping agents. To realize this, flame aerosol synthesis (FAS) is a promising method due to its short particle residence time, tunable redox environment, and good scalability. Herein, the one-step FAS of NiFe-P is reported for the first time. With the controlled coformation of carbon, interlaced NiFe-P nanoplates and <5 nm NiFe-P nanoparticles are selectively synthesized on nickel foam in 10 min. At the anodic potential of OER, NiFe-P transforms into highly active (oxy)hydroxides in situ by surface oxidation and dephosphorylation. The overpotential of the optimal film at 500 mA cm–2 increases at only 0.28 mV h–1 over 100 h, making it among the most durable NiFe-based catalysts reported. Post-OER cyclic voltammetry, double-layer capacitance, and inductively coupled plasma mass spectrometry (ICP-MS) measurements indicate performance degradation to be mainly caused by the selective leaching of Fe from the (oxy)hydroxides. Counterintuitively, slight structural instability of the films induced by the electrochemical removal of carbon enhances durability by keeping a relatively stable surface Fe content through a self-refreshing mechanism.

Selective oxidation of silanes into silanols with water using [MnBr(CO)5] as a precatalyst.

The development of earth-abundant catalysts for the selective conversion of silanes to silanols with water as an oxidant generating valuable hydrogen as the only by-product continues to be a challenge. Here, we demonstrate that [MnBr(CO)5] is a highly active precatalyst for this reaction, operating under neutral conditions and avoiding the undesired formation of siloxanes. As a result, a broad substrate scope, including primary and secondary silanes, could be converted to the desired products. The turnover performances of the catalyst were also examined, yielding a maximum TOF of 4088 h-1. New light was shed on the debated mechanism of the interaction between [MnBr(CO)5] and Si-H bonds based on the reaction kinetics (including KIEs of PhMe2SiD and D2O) and spectroscopic techniques (FT-IR, GC-TCD, 1H-, 29Si-, and 13C-NMR). The initial activation of [MnBr(CO)5] was found to result from the formation of a manganese(i) hydride species and R3SiBr, and the experimental data are most consistent with a catalytic cycle comprising a cationic tricarbonyl Mn(i) unit as the active framework.

Synthesis, structural characterization and catalytic application of zinc and cadmium sulfur complexes with imidazol-2-ylidene-N’-phenylthiourea ligand scaffold

We report the synthetic and structural studies of a series of zinc metal complexes, [(ImRNCSN(H)Ph)2ZnX2] (R = Mesityl (Mes), X = Cl (1a), Br (1b), I (1c); R = 2,6-Diisopropylphenyl (Dipp), X = Cl (2a), Br (2b), I (2c)) and the cadmium metal complexes [(ImRNCSN(H)Ph)2CdX2] (R = Mes, X = Cl (3a), I (3b)] and [(ImRNCSN(H)Ph)CdX]2 [R = Dipp, X = Cl (4a), I (4b)). The solid-state structures of metal complexes 1c, 2c, 3a, 4a, and 4b were established by single-crystal X-ray diffraction analysis. The zinc complexes 1c, 2c, and cadmium complex 3a are isostructural in solid-state, and in each case, the metal ion is ligated with two ligand moieties in a monodentate fashion via the sulfur atom. Despite similar coordination features, they exhibited a marked variation in the orientation of phenylthiourea scaffold as well as hydrogen-bonding interactions. The solid-state structures of cadmium complexes 4a and 4b involve a centrosymmetric dimer containing four-membered ring –[Cd-X−]2, formed by μ2-coordination of the halide group on each cadmium atom. In all the complexes, the metal ion (Zn2+/Cd2+) adopts a distorted tetrahedral MS2X2 environment. Additionally, the catalytic activity of [(ImMesNCSN(H)Ph)2ZnI2] (1c) as an active pre-catalyst is reported in the NH addition of amines to readily available carbodiimides to produce a series of substituted guanidine derivatives in an excellent yield. The zinc complex 1c showed very good conversion and tolerance of a broad and valuable substrate scope during the guanidine formation.

Synthesis of PdII Triazolylidene Complexes via an Unusual Csp2‐Csp2 Decoupling Reaction: Applications in α‐Arylation of Amide and Suzuki‐Miyaura Coupling Reactions

AbstractMononuclear PdII complexes bearing mixed MIC/Py/PPh3 donor set ligands are presented starting from a bis‐triazolium salt featuring 4,4’‐substitution pattern of central biphenyl ring. The mononuclear PEPPSI (pyridine enhanced precatalyst preparation, stabilization and initiation) type complexes bearing triazolylidene donor ligand have been synthesized via an unusual Csp2‐Csp2 decoupling reaction. The complexes have been characterized by 1H, 13C{1H} NMR spectroscopy and mass spectrometry. Two of the complexes have also been structurally characterized by single crystal XRD. All the complexes appeared as active precatalysts in α‐arylation of amide and Suzuki‐Miyaura coupling reactions. Catalytic outcomes clearly indicate the superior activities of the PdII complexes with mixed MIC/PPh3 donor set ligands compared to the corresponding PEPPSI type complexes in α‐arylation of oxindole.

Role of Noble- and Base-Metal Speciation and Surface Segregation in Ni2–xRhxP Nanocrystals on Electrocatalytic Water Splitting Reactions in Alkaline Media

Transition-metal phosphides have proven to be surprisingly active electrocatalysts for electrochemical water splitting, but the nature of the “active” catalyst depends strongly on the solution pH, the identity of the metals, and whether the reactions are anodic [oxygen evolution reaction (OER)] or cathodic [hydrogen evolution reaction (HER)]. In order to understand the origin of this activity, the synthesis of well-defined, compositionally controlled precatalysts is needed, as are detailed catalytic studies and physicochemical characterization/activity assessment of catalysts at different stages. While base-metal phosphides of Ni and Co have the advantage of being earth-abundant, in alkaline media, they are less active and less stable than noble-metal phosphides such as Rh2P. As a means to combine the abundant nature of base metals with the activity and stability of noble metals, the first synthesis of colloidal Ni2–xRhxP nanocrystals by arrested precipitation routes is reported along with their composition-dependent activity for electrocatalytic HER and OER. Phase-pure samples of Ni2–xRhxP were realized at the Ni-rich (hexagonal, Fe2P-type) end (x = 0.00, 0.25, 0.50) and Rh-rich (cubic, antifluorite-type) end (x = 1.75, 2.00). When assessed in terms of current density normalized to electrochemical surface area (ECSA) at a fixed potential, the most active precatalyst for OER is Ni1.75Rh0.25P, and for HER, it is Rh1.75Ni0.25P. Evaluation of X-ray photoelectron spectroscopy, transmission electron microscopy/energy-dispersive spectroscopy and ECSA data before and after 10 h stability runs were performed. The data reveal surface compositions to be considerably richer in Ni and poorer in Rh and P relative to the bulk composition, particularly for Ni0.25Rh1.75P, where the surface ratio of Ni/Rh is nearly 2:1 and increases to 4:1 after HER catalysis. In all cases, surface phosphorus is completely depleted post catalysis, suggesting a sacrificial role for phosphide under alkaline conditions. Moreover, the activity of “Rh1.75Ni0.25P” for HER decreases over time, even as the ECSA continues to rise, attributed to a decrease in the more active and stable Rh sites relative to Ni on the surface. In contrast, the enhancement in OER activity of Ni2P with 12.5% Rh incorporation is attributed to restructuring upon phase segregation of Rh, suggesting that the noble metal may also play a sacrificial role and not directly participate in OER catalysis. The roles of minority noble metals (Rh) in base-metal phosphides for OER and of minority base metals in noble-metal (Rh) phosphides for HER are discussed in light of related data on Co2–xRhxP.

Synthesis, Catalytic Activity and Comparative Leaching Studies of Calix[8]arene‐Supported Pd‐NHC Complexes for Suzuki‐Miyaura Cross‐Couplings

AbstractA rapid and scalable synthesis of supported NHC−Pd(II)‐pyridine complexes on a benzyloxycalix[8]arene macrocycle is reported. Their subsequent use in Suzuki‐Miyaura benchmark reactions led to the optimisation of the nature of the ligands around the metal centre, delivering two very active precatalysts. They both promote the cross‐coupling of challenging API precursors at low catalytic loadings, when used as insoluble species in EtOH as a green reaction solvent. Moreover, their activity has been shown to be comparable or even superior to that of more conventional homogeneous catalysts. Of main importance, a simple filtration of the insoluble supported catalysts after reaction afforded the lowest Pd contamination values in the target products, in some cases directly approaching the levels authorised by the industrial regulations. Offering furthermore the possibility of easy palladium recovery in the current context of its overconsumption, we are convinced that these calixarene‐supported NHC‐PEPPSI Pd complexes are valuable tools for the fine chemical industry, to prepare metal‐free functionalised biaryl compounds in high yields, ranging from 76 to 94%.magnified image

Aluminium alkyl complexes supported by imino-phosphanamide ligand as precursors for catalytic guanylation reactions of carbodiimides.

Herein, we report the synthesis, characterisation, and application of three aluminium alkyl complexes, [κ2-{NHIRP(Ph)NDipp}AlMe2] (R = Dipp (2a), Mes (2b); tBu (2c), Dipp = 2,6-diisopropylphenyl, Mes = mesityl, and tBu = tert-butyl), supported by unsymmetrical imino-phosphanamide [NHIRP(Ph)NDipp]− [R = Dipp (1a), Mes (1b), tBu (1c)] ligands as molecular precursors for the catalytic synthesis of guanidines using carbodiimides and primary amines. All the imino-phosphanamide ligands 1a, 1b and 1c were prepared in good yield from the corresponding N-heterocyclic imine (NHI) with phenylchloro-2,6-diisopropylphenylphosphanamine, PhP(Cl)NHDipp. The aluminium alkyl complexes 2a, 2b and 2c were obtained in good yield upon completion of the reaction between trimethyl aluminium and the protic ligands 1a, 1b and 1c in a 1 : 1 molar ratio in toluene via the elimination of methane, respectively. The molecular structures of the protic ligands 1b and 1c and the aluminium complexes 2a, 2b and 2c were established via single-crystal X-ray diffraction analysis. Complexes 2a, 2b and 2c were tested as pre-catalysts for the hydroamination/guanylation reaction of carbodiimides with aryl amines to afford guanidines at ambient temperature. All the aluminium complexes exhibited a high conversion with 1.5 mol% catalyst loading and broad substrate scope with a wide functional group tolerance during the guanylation reaction. We also proposed the most plausible mechanism, involving the formation of catalytically active three-coordinate Al species as the active pre-catalyst.

Markovnikov-selective double hydrosilylation of challenging terminal aryl alkynes under cobalt and iron catalysis.

Geminal bis(silanes) are unique compounds with interesting properties. The most straightforward way to access them is double hydrosilylation of alkynes, which was established only recently. Previous articles about transition metal-catalysed double hydrosilylation show that terminal aryl alkynes are a challenge. We report on cobalt(II) and iron(III) complexes with the easy-to-synthesise N,N,N-tridentate hydrazone ligand being active precatalysts in Markovnikov-selective double hydrosilylation of terminal aryl alkynes. The influence of the hydrazone ligand structure and the potential role of the sodium triethylborohydride activator were studied. Sets of geminal bis(silanes) with two identical or different silyl groups were synthesised, showing the applicability of the reported method.

Epoxidation catalysts prepared by encapsulation of molybdenum hexacarbonyl in UiO-66(Zr/Hf)-type metal-organic frameworks

The confinement and catalytic behavior of Mo(CO)6 species inside UiO-66 (zirconium and hafnium) metal-organic frameworks (MOFs) have been investigated by means of multitechnique characterization and catalytic olefin epoxidation. Mo(CO)6 was encapsulated in nanocrystalline MOFs by solvothermal and vapor phase impregnation methods (STI and VPI, respectively), resulting in Mo loadings of 2.0–8.8 wt% (STI) or 15 wt% (VPI). Powder X-ray diffraction, SEM-EDS, N2 adsorption, FT-IR and 13C{1H} CP MAS NMR collectively confirmed immobilization within the pore spaces of the hosts, which maintained their bulk crystallinity and crystal morphologies. CO resonances in the 13C{1H} CP MAS NMR spectra were assigned to hexacarbonyl guest molecules located in the larger pore spaces, such as the octahedral cavities (for STI and VPI samples), and in more restricted environments such as the tetrahedral cavities (for the VPI sample). FT-IR spectra displayed the characteristic pattern of νCO stretching modes for an octahedral symmetry molecule slightly perturbed by interaction of one of the carbonyl groups with the MOF support. The spectra evidenced the formation of a weak hydrogen bonding interaction of the type μ3-OH···OCMo(CO)5 involving the μ3-OH groups that are exclusively present in the tetrahedral cavities of the UiO-66 structure. The Mo(CO)6 loaded MOFs are active and reusable pre-catalysts for cis-cyclooctene epoxidation, exhibiting excellent epoxide selectivity (up to quantitative epoxide yield within 1 h reaction) and tert-butyl hydroperoxide efficiency. Catalyst recycling and retention of structural integrity were demonstrated for UiO-66(Hf) loaded with 8.8 wt% Mo by the STI method. The UiO-66(Hf) host may be a better catalyst support than its Zr counterpart due its smaller crystallite size (≈100 nm) and higher defectivity. The substrate scope was broadened for Mo(8.8-STI)/Hf-MOF which promoted the epoxidation of biobased olefins (methyl oleate and dl-limonene) and oxidative dehydrogenation of cyclooctanol to cyclooctanone.