Salt forms of amides: protonation of acetanilide.

Treating the amide acetanilide (N-phenylacetamide, C8H9NO) with aqueous strong acids allowed the structures of five hemi-protonated salt forms of acetanilide to be elucidated. N-(1-Hydroxyethylidene)anilinium chloride-N-phenylacetamide (1/1), [(C8H9NO)2H][Cl], and the bromide, [(C8H9NO)2H][Br], triiodide, [(C8H9NO)2H][I3], tetrafluoroborate, [(C8H9NO)2H][BF4], and diiodobromide hemi(diiodine), [(C8H9NO)2H][I2Br]·0.5I2, analogues all feature centrosymmetric dimeric units linked by O-H...O hydrogen bonds that extend into one-dimensional hydrogen-bonded chains through N-H...X interactions, where X is the halide atom of the anion. Protonation occurs at the amide O atom and results in systematic lengthening of the C=O bond and a corresponding shortening of the C-N bond. The size of these geometric changes is similar to those found for hemi-protonated paracetamol structures, but less than those in fully protonated paracetamol structures. The bond angles of the amide fragments are also found to change on protonation, but these angular changes are also influenced by conformation, namely, whether the amide group is coplanar with the phenyl ring or twisted out of plane.

A monoclinic polymorph of chloro-thia-zide.

A new polymorph of the diuretic chloro-thia-zide, 6-chloro-1,1-dioxo-2H-1,2,4-benzo-thia-zine-7-sulfonamide, C7H6ClN3O4S2, is described. Crystallized from basic aqueous solution, this monoclinic polymorph is found to be less thermodynamically favoured than the known triclinic polymorph and to feature only N-H⋯O type inter-molecular hydrogen bonds as opposed to the N-H⋯O and N-H⋯N type hydrogen bonds found in the P1 form.

Application of Bis(amido)alkyl Magnesiates toward the Synthesis of Molecular Rubidium and Cesium Hydrido-magnesiates.

Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN'2alkyl]∞, where N' is the simple heteroamide -N(SiMe3)(Dipp), and alkyl is nBu or CH2SiMe3, are reported. More stable than their nBu analogues, the reactivities of the CH2SiMe3 magnesiates toward 1,4-cyclohexadiene are revealed. Though both reactions produce target hydrido-magnesiates [(AM)MgN'2H]2 in crystalline form amenable to X-ray diffraction study, the cesium compound could only be formed in a trace quantity. These studies showed that the bulk of the -N(SiMe3)(Dipp) ligand was sufficient to restrict both compounds to dimeric structures. Bearing some resemblance to inverse crown complexes, each structure has [(AM)(N)(Mg)(N)]2 ring cores but differ in having no AM-N bonds, instead Rb and Cs complete the rings by engaging in multihapto interactions with Dipp π-clouds. Moreover, their hydride ions occupy µ3-(AM)2Mg environments, compared to µ2-Mg2 environments in inverse crowns.

Mechanistic Basis of the Cu(OAc)2 Catalyzed Azide-Ynamine (3 + 2) Cycloaddition Reaction.

The Cu-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is used as a ligation tool throughout chemical and biological sciences. Despite the pervasiveness of CuAAC, there is a need to develop more efficient methods to form 1,4-triazole ligated products with low loadings of Cu. In this paper, we disclose a mechanistic model for the ynamine-azide (3 + 2) cycloadditions catalyzed by copper(II) acetate. Using multinuclear nuclear magnetic resonance spectroscopy, electron paramagnetic resonance spectroscopy, and high-performance liquid chromatography analyses, a dual catalytic cycle is identified. First, the formation of a diyne species via Glaser-Hay coupling of a terminal ynamine forms a Cu(I) species competent to catalyze an ynamine-azide (3 + 2) cycloaddition. Second, the benzimidazole unit of the ynamine structure has multiple roles: assisting C-H activation, Cu coordination, and the formation of a postreaction resting state Cu complex after completion of the (3 + 2) cycloaddition. Finally, reactivation of the Cu resting state complex is shown by the addition of isotopically labeled ynamine and azide substrates to form a labeled 1,4-triazole product. This work provides a mechanistic basis for the use of mixed valency binuclear catalytic Cu species in conjunction with Cu-coordinating alkynes to afford superior reactivity in CuAAC reactions. Additionally, these data show how the CuAAC reaction kinetics can be modulated by changes to the alkyne substrate, which then has a predictable effect on the reaction mechanism.

Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine.

Recently main group compounds have stepped into the territory of precious transition metal compounds with respect to utility in the homogeneous catalysis of fundamentally important organic transformations. Inspired by the need to promote more sustainability in chemistry because of their greater abundance in nature, this change of direction is surprising since main group metals generally do not possess the same breadth of reactivity as precious transition metals. Here, we introduce the dihydropyridylsodium compound, Na-1,2-tBu-DH(DMAP), and its monomeric variant [Na-1,2-tBu-DH(DMAP)]·Me6TREN, and demonstrate their effectiveness in transfer hydrogenation catalysis of the representative alkene 1,1-diphenylethylene to the alkane 1,1-diphenylethane using 1,4-cyclohexadiene as hydrogen source [DMAP = 4-dimethylaminopyridine; Me6TREN = tris(N,N-dimethyl-2-aminoethyl)amine]. Sodium is appealing because of its high abundance in the earth's crust and oceans, but organosodium compounds have been rarely used in homogeneous catalysis. The success of the dihydropyridylsodium compounds can be attributed to their high solubility and reactivity in organic solvents.

Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes.

Molecular heterobimetallic hydride complexes of lanthanide (Ln) and main-group (MG) metals exhibit chemical properties unique from their monometallic counterparts and are highly reactive species, making their synthesis and isolation challenging. Herein, molecular Ln/Al heterobimetallic trihydrides [Ln(Tp)2(µ-H)2Al(H)(N″)] [2-Ln; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; N″ = N(SiMe3)2] have been synthesized by facile insertion of aminoalane [Me3N·AlH3] into the Ln-N amide bonds of [Ln(Tp)2(N″)] (1-Ln). Thus, this is a simple synthetic strategy to access a range of Ln/Al hydrides. Reactivity studies demonstrate that 2-Ln is a heterobimetallic hydride, with evidence for the cooperative nature of 2-Ln shown by the catalytic amine-borane dehydrocoupling under ambient conditions in contrast to its monomeric counterparts.

Isostructural behaviour in ammonium and potassium salt forms of sulfonated azo dyes.

The structures of five ammonium salt forms of monosulfonated azo dyes, derivatives of 4-(2-phenyldiazen-1-yl)benzenesulfonate, with the general formula [NH4][O3S(C6H4)NN(C6H3)RR']·XH2O [R = OH, NH2 or N(C2H4OH)2; R' = H or OH] are presented. All form simple layered structures with alternating hydrophobic (organic) and hydrophilic (cation, solvent and polar groups) layers. To assess for isostructural behaviour of the ammonium cation with M+ ions, the packing of these structures is compared with literature examples. To aid this comparison, the corresponding structures of four potassium salt forms of the monosulfonated azo dyes are also presented herein. Of the five ammonium salts it is found that three have isostructural equivalents. In two cases this equivalent is a potassium salt form and in one case it is a rubidium salt form. The isostructurality of ion packing and of unit-cell symmetry and dimensions tolerates cases where the ammonium ions form somewhat different interaction types with coformer species than do the potassium or rubidium ions. No sodium salt forms are found to be isostructural with any ammonium equivalent. However, similarities in the anion packing within a single hydrophobic layer are found for a group that consists of the ammonium and rubidium salt forms of one azo anion species and the sodium and silver salt forms of a different azo species.

Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method.

The synthesis of multivariate metal-organic frameworks (MOFs) is a well-known method for increasing the complexity of porous frameworks. In these materials, the structural differences of the ligands used in the synthesis are sufficiently subtle that they can each occupy the same site in the framework. However, multivariate or ligand scrambling approaches are rarely used in the synthesis of porous metal-organic polyhedra (MOPs) - the molecular equivalent of MOFs - despite the potential to retain a unique intrinsic pore from the individual cage while varying the extrinsic porosity of the material. Herein we directly synthesise scrambled cages across two families of lantern-type MOPs and find contrasting effects on their gas sorption properties. In one family, the scrambling approach sees a gradual increase in the BET surface area with the maximum and minimum uptakes associated with the two pure homoleptic cages. In the other, the scrambled materials display improved surface areas with respect to both of the original, homoleptic cages. Through analysis of the gas sorption isotherms, we attribute this effect to the balance of micro- and mesoporosity within the materials, which varies as a result of the scrambling approach. The gas uptake of the materials presented here underscores the tunability of cages that springs from their combination of intrinsic, extrinsic, micro- and meso-porosities.

Synthesis of 2,6-trans-Tetrahydropyrans Using a Palladium-Catalyzed Oxidative Heck Redox-Relay Strategy.

The C-aryl-tetrahydropyran motif is prevalent in nature in a number of natural products with biological activity; however, this challenging architecture still requires novel synthetic approaches. We demonstrate the application of a stereoselective Heck redox-relay strategy for the synthesis of functionalized 2,6-trans-tetrahydropyrans in excellent selectivity in a single step from an enantiopure dihydropyranyl alcohol, proceeding through a novel exo-cyclic migration. The strategy has also been applied to the total synthesis of a trans-epimer of the natural product centrolobine in excellent yield and stereoselectivity.

Modification of a Common ß-diketiminate NacNac Framework via Sequential Lithiation and Small Molecule Insertion.

A widely utilised class of ligands in synthesis and catalysis, ß-diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ-C-H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6-diisopropylphenyl-ß-methyldiketimine [NacNacH (Me, Dipp)]. Lithiation to give NacNacLi, followed by reactions with isocyanates, isothiocyanates and a carbodiimide, have afforded a series of tripodal NacNac variants having N,N,N,O; N,N,N,S; or N,N,N,N potential dentation sites, many of which have been crystallographically characterised. Distinct ligating modes of these new ligands have been elucidated through the crystal structures of their lithiated derivatives.

Synthesis and Reactivity of an Aluminium N-heterocyclic Aminal.

Tethered N-heterocyclic carbenes (NHCs) are an emerging class of ligand, as they feature all the desirable aspects of NHCs (ease of synthesis, high tunabilty) but also enable metal-ligand cooperativity when combined with Lewis acidic metal centres due to the donor-acceptor nature of the complexes formed. Herein we report a simple ethoxy-tethered NHC for the stabilisation of Al(III) hydrides, resulting in the unexpected formation of a bicyclic N-heterocyclic aminal (1). Compound 1 behaves as a metal hydride, capable of reducing benzophenone and carbodiimide to yield compounds 2 and 3, respectively. Furthermore, we show that 1 behaves as an efficient catalyst in the dehydrocoupling of amine-boranes due to the hemi-labile nature of the supporting ligand.

Isolable rubidium and caesium derivatives of common organic carbonyl compounds.

Light alkali metal (Li, Na, K) amides have a long history of synthetic utility, but heavier (Rb, Cs) congeners have barely been studied. This study reveals remarkable structurally complex outcomes of reacting AM(HMDS) (AM = Rb, Cs; HMDS = hexamethyldisilazide) with benzaldehyde and acetophenone. Though complicated, reactions give a diversity of eye-catching isolated products, an enolate with a hexagonal prismatic network, two dienolates with distinct extended ladder motifs, and two ß-imino-alkoxides comprising zig-zag chains of metal-oxygen bonds in infinite cages.

Atom-economic access to cationic magnesium complexes.

Cationic alkaline-earth complexes attract interest for their enhanced Lewis acidity and reactivity compared with their neutral counterparts. Synthetic protocols to these complexes generally utilize expensive specialized reagents in reactions generating multiple by-products. We have studied a simple ligand transfer approach to these complexes using (NacNac)MgR and ER3 (NacNac = ß-diketiminate anion; E = group 13 element; R = aryl/amido anion) which demonstrates high atom economy, opening up the ability to target these species in a more sustainable manner. The success of this methodology is dependent on the identity of the group 13 element with the heavier elements facilitating faster ligand exchange. Furthermore, while this reaction is successful with aromatic ligands such as phenyl and pyrrolyl, the secondary amide piperidide (pip) fails to transfer, which we attribute to the stronger 3-centre-4-electron dimerization interaction of Al2(pip)6.

A Hierarchy of Ligands Controls Formation and Reaction of Aryl Radicals in Pd-Catalyzed Ground-State Base-Promoted Coupling Reactions.

Palladium salts and complexes were tested separately and in the presence of added ligands as potential sources of aryl radicals in ground-state coupling reactions of aryl halide with arenes under basic conditions (KOtBu). Our recently developed assay for aryl radicals was employed to test for aryl radicals. In this assay, aryl radicals derived from the test substrate, 1-iodo-2,6-dimethylbenzene 7, undergo base-promoted homolytic aromatic substitution (BHAS) with benzene to produce 2,6-dimethylbiphenyl 8 and biphenyl 9 in an approximately 1:4 ratio as well as m-xylene 10. The biphenyl arises from a diagnostic radical transfer reaction with the solvent benzene. Using substrate 7 with a range of Pd sources as potential initiators led to formation of 8, 9, and 10 in varying amounts. However, when any one of a range of diphosphinoferrocenes (e.g., dppf or dippf) or BINAP or the monophosphine, diphenylphosphinoferrocene, was added as a ligand to Pd(OAc)2, the ratio of [2,6-dimethylbiphenyl 8: biphenyl 9] moved decisively to that expected from the BHAS (radical) pathway. Further studies were conducted with dppf. When dppf was added to each of the other Pd sources, the ratio of coupled products was also diverted to that expected for radical BHAS chemistry. Deuterium isotope studies and radical trap experiments provide strong additional support for the involvement of aryl radicals. Accordingly, under these ground-state conditions, palladium sources, in the presence of defined ligands, convert aryl iodides to aryl radicals. A rationale is proposed for these observations.

A structural comparison of salt forms of dopamine with the structures of other phenylethylamines.

The structures of four salt forms of dopamine are reported. These are dopamine [2-(3,4-dihydroxyphenyl)ethan-1-aminium] benzoate, C8H12NO2+·C7H5O2-, I, dopamine 4-nitrobenzoate, C8H12NO2+·C7H4NO4-, II, dopamine ethanedisulfonate, 2C8H12NO2+·C2H4O6S22-, III, and dopamine 4-hydroxybenzenesulfonate monohydrate, C8H12NO2+·C6H5O4S-·H2O, IV. In all four structures, the dopamine cation adopts an extended conformation. Intermolecular interaction motifs that are common in the salt forms of tyramine can be found in related dopamine structures, but hydrogen bonding in the dopamine structures appear to be more variable and less predictable than for tyramine. Packing analysis discovered three dopamine-containing groups of structures that can be described as isostructural with regards to the cation positions. Two of these groups contain both dopamine and tyramine species, and one of these is also highly variable in other ways too, containing anhydrous and hydrated forms, different anion types and ionized and neutral phenylethylamine species. As such, the group illustrates that packing behaviour can be robust and similar even where intermolecular interactions such as hydrogen bonds are very different.

Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs.

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.

Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO2.

Three distinct routes are reported to the soluble, dihydridoaluminate compounds, AM[Al(NONDipp )(H)2 ] (AM=Li, Na, K, Rb, Cs; [NONDipp ]2- =[O(SiMe2 NDipp)2 ]2- ; Dipp=2,6-iPr2 C6 H3 ) starting from the alkali metal aluminyls, AM[Al(NONDipp )]. Direct H2 hydrogenation of the heavier analogues (AM=Rb, Cs) produced the first examples of structurally characterized rubidium and caesium dihydridoaluminates, although harsh conditions were required for complete conversion. Using 1,4-cyclohexadiene (1,4-CHD) as an alternative hydrogen source in transfer hydrogenation reactions provided a lower energy pathway to the full series of products for AM=Li-Cs. A further moderation in conditions was noted for the thermal decomposition of the (silyl)(hydrido)aluminates, AM[Al(NONDipp )(H)(SiH2 Ph)]. Probing the reaction of Cs[Al(NONDipp )] with 1,4-CHD provided access to a novel inverse sandwich complex, [{Cs(Et2 O)}2 {Al(NONDipp )(H)}2 (C6 H6 )], containing the 1,4-dialuminated [C6 H6 ]2- dianion and representing the first time that an intermediate in the commonly utilized oxidation process of 1,4-CHD to benzene has been trapped. The synthetic utility of the newly installed Al-H bonds has been demonstrated by their ability to reduce CO2 under mild conditions to form the bis-formate AM[Al(NONDipp )(O2 CH)2 ] compounds, which exhibit a diverse series of eyecatching bimetallacyclic structures.

Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy.

Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4-dicyclohexadiene. Unusually, this has been achieved using s-block pre-catalysts, namely 1-metallo-2-tert-butyl-1,2-dihydropyridines, 2-tBuC5 H5 NM, M(tBuDHP), where M=Li-Cs. Reactions have been monitored in C6 D6 and tetrahydrofuran-d8 (THF-d8 ). A definite trend is observed in catalyst efficiency with the heavier alkali metal tBuDHPs outperforming the lighter congeners. In general, Cs(tBuDHP) is the optimal pre-catalyst with, in the best cases, reactions producing quantitative yields of amines in minutes at room temperature using 5 mol % catalyst. Supporting the experimental study, Density Functional Theory (DFT) calculations have also been carried out which reveal that Cs has a pathway with a significantly lower rate determining step than the Li congener. In the postulated initiation pathways DHP can act as either a base or as a surrogate hydride.

Porous Metal-Organic Cages Based on Rigid Bicyclo[2.2.2]oct-7-ene Type Ligands: Synthesis, Structure, and Gas Uptake Properties.

Three new ligands containing a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit have been used to assemble lantern-type metal-organic cages with the general formula [Cu4 L4 ]. Functionalisation of the backbone of the ligands leads to distinct crystal packing motifs between the three cages, as observed with single-crystal X-ray diffraction. The three cages vary in their gas sorption behaviour, and the capacity of the materials for CO2 is found to depend on the activation conditions: softer activation conditions lead to superior uptake, and one of the cages displays the highest BET surface area found for lantern-type cages so far.

Serendipitous Enhancement of the Dimensionality in Diketopyrrolopyrroles through O-Substitution.

We report for the first time the crystal structure of an O-substituted diketopyrrolopyrrole and further evaluate computationally the ability of this higher-dimensionality system to act as a charge transfer mediator in optoelectronic devices.