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The solid-state structure of sixteen triphilic triazolium salts with different anions is considered in terms of the potentially competing factors driving organisation.

International audience; The reaction between [IrCl(COD)]2 and dppe in a 1:2 ratio was investigated in detail under three different conditions. [IrCl(COD)(dppe)], 1, is formed at room temperature in the absence of base. In the presence of a strong base at room temperarture, hydride complexes that retain the carbocyclic ligand in the coordination sphere are generated. In isopropanol, 1 is converted into [IrH(1,2,5,6-η2:η2-COD)(dppe)] (2) on addition of KOtBu, with k12 = (1.11±0.02)·10-4 s-1, followed by reversible isomerisation to [IrH(1-κ-4,5,6-η3-C8H12)(dppe)] (3) with k23 = (3.4±0.2)·10-4 s-1 and k32 = (1.1±0.3)·10-5 s-1 to yield an equilibrium 5:95 mixture of 2 and 3. However, when no hydride source is present in the strong base (KOtBu in benzene or toluene), the COD ligand in 1 is deprotonated, followed by β-H elimination of an IrI-C8H11 intermediate, which leads to complex [IrH(1-κ-4,5,6-η3-C8H10)(dppe)] (4) selectively. This is followed by its reversible isomerisation to 5, which features a different relative orientation of the same ligands (k45 = (3.92±0.11)·10-4 s-1; k54 = (1.39±0.12)·10-4 s-1 in C6D6), to yield an equilibrated 32:68 mixture of 4 and 5. DFT calculations assisted in the full rationalization of the selectivity and mechanism of the reactions, yielding thermodynamic (equilibrium) and kinetic (isomerization barriers) parameters in excellent agreement with the experimental values. Finally, in the presence of KOtBu and isopropanol at 80 °C, 1 is tranformed selectively to K[IrH4(dppe)] (6), a salt of an anionic tetrahydride complex of IrIII. This product is also selectively generated from 2, 3, 4 and 5 and H2 at room temperature, but only when a strong base is present. These results provide an insight into the catalytic action of [IrCl(LL)(COD)] complexes in the hydrogenation of polar substrates in the presence of a base. more...

“GaOTf” is a simple, convenient source of low‐valent gallium for synthetic chemistry and catalysis. However, little is currently known about its composition or reactivity. In this work, 71Ga NMR spectroscopy shows the presence of [Ga(arene)n]+ salts on oxidation of Ga metal with AgOTf in arene solvents. However, a more complex picture of speciation is uncovered by X‐ray diffraction studies. In all cases, mixed‐valence compounds containing Ga‐arene and Ga‐OTf coordination motifs, in addition to an unusual “naked” [Ga]+ ion, are found. Addition of 18‐crown‐6 allows for the isolation of a discrete GaI crown complex. Evidence of a potential intermediate in the formation of “GaOTf” has been isolated in the form of the bimetallic silver(I)/gallium(I) cluster anion [Ag4{Ga(OTf)3}4(μ‐Ga)6(OTf)4]2−., Gallium(I) triflate is a promising new source of low‐valent gallium for synthesis and catalysis. However, little is known about its composition and structural chemistry. Here it is demonstrated that speciation is quite complex in this system, with compounds containing Ga in multiple oxidation states being isolated from arene solutions. more...

The preparation of mixtures of ionic liquids (ILs) represents an attractive strategy to tune their properties, an important aspect of which is to understand how the structure of the bulk varies with composition. In this study, small-angle neutron scattering (SANS) was used to probe mixtures of methylimidazolium-based ionic liquids [Cnmim][Tf2N] with [C2mim][Tf2N]) (n = 4, 6, 8 and 10) and of [Cmmim][Tf2N] with [C12mim][Tf2N] (m = 2, 4, 6 and 8). Mixtures were prepared in both contrasts, which is to say that one component would be fully hydrogenated while the other was fully deuterated, and vice versa. Data were fitted using a range of appropriate models, of which the Teubner-Strey model provided most useful information and the pure materials showed a nascent Polar Non-polar Peak (PNPP) for n = 6, which became more evident as n increased. In the mixtures [Cnmim]x[C2mim]1−x[Tf2N], the PNPP was evident for n = 10 and 8, nascent for n = 6 and absent for n = 4, with percolation showing a very strong dependence on the chain length of the added IL, [Cnmim][Tf2N]. In contrast, while the ability of [C12mim][Tf2N] to form percolated structures was damped when mixed with [Cmmim][Tf2N], as m increased from 2 to 6, this effect was less strong. However, data obtained for mixtures of [C12mim][Tf2N] and [C8mim][Tf2N], both of which percolate as pure materials, did not fit easily in any of the models applied to the previous systems and gave results that depended on the contrast used. Complementary small-angle X-ray scattering (SAXS) data, however, showed the expected evolution and behaviour of the PNPP, COP and CP, revealing that the unexpected observations were due to an adventitious matching out of isotopic contrasts. As well as revealing details of the structures of these IL mixtures, the results also point to complementary strategies for generating bulk percolated structures as a function of cation chain length. more...

The gas-liquid interface of ionic liquids (ILs) is critically important in many applications, for example, in supported IL phase (SILP) catalysis. Methods to investigate the interfacial structure in these systems will allow their performance to be improved in a rational way. In this study, reactive-atom scattering (RAS), surface tension measurements, and molecular dynamics (MD) simulations were used to study the vacuum interface of mixtures of partially fluorinated and normal alkyl ILs. The underlying aim was to understand whether fluorinated IL ions could be used as additives to modify the surface structure of one of the most widely used families of alkyl ILs. The series of ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C more...

Advanced weakly coordinating anions (WCAs) significantly facilitate synthesis of various exotic chemical compounds and novel, potentially useful materials. One of such anions - [Al{OC(CF3)3}4]-, denoted [Al(ORF)4]-, appears particularly convenient, as it can be easily prepared from the commercially available alanates and HOC(CF3)3. Here we present a thorough characterization of a series of solvent-free M[Al(ORF)4] salts, M = Li-Cs, Ag, NH4, N2H5 and N2H7, and related compounds of monovalent cations, which are crucial starting materials for further work with these species. Notably, the corresponding synthetic protocols are updated by an improved method for fast, facile and easily scalable synthesis of Li[Al(ORF)4], which remains the most useful primary source of the anion. The physico-chemical properties of these salts including crystal structures, thermal stability by TG/DSC, vibrational spectra as well as solubility are discussed in a systematic fashion. more...

The speciation, conformation, and reactivity of transition metal complexes at the gas–liquid interface are poorly understood, yet the potential is high for observing chemistry unique to this anisot... more...

Palladium catalysed cross-couplings reactions have been a dominant method in synthetic chemistry for decades. Despite this, the role of the solvent is often taken for granted and poorly understood. Regulations affecting some the most frequently used solvents for cross-coupling reactions are accelerating current trends towards using new types of solvents. In this review, the fundamental interactions between solvent and catalyst are explained so that it may inform the rational selection of high performance and safe solvents. The popular cross-coupling methodologies are addressed (Suzuki, Stille, Kumada, Negishi, Hiyama, Heck, Sonogashira, and Buchwald–Hartwig reactions) and novel solvents introduced. more...

ispartof: FARADAY DISCUSSIONS vol:220 issue:0 pages:144-178 ispartof: location:England status: published

Advanced weakly coordinating anions (WCAs) significantly facilitate synthesis of various exotic chemical compounds and novel, potentially useful materials. One of such anions - [Al{OC(CF

The vacuum–liquid interfaces of a number of ionic-liquid mixtures have been investigated using the combination of reactive-atom scattering with laser-induced fluorescence detection (RAS-LIF), selected surface tension measurements, and molecular dynamics (MD) simulations. The mixtures are based on the widespread 1-alkyl-3-methylimidazolium ([Cnmim]+) cation, including mixed cations which differ in chain length or chemical functionality with a common anion; and different anions for a common cation. RAS-LIF results imply that the surface compositions exhibit a general form of non-stoichiometric behaviour that mimics the well-known Henry’s and Raoult’s laws at low and high mole fraction, respectively. The extended Langmuir model provides a moderately good single-parameter fit, but higher-order terms are required for an accurate description. The quantitative relationship between RAS-LIF and surface tension, which probes the surface composition only indirectly, is explored for mixtures of [C2mim]+ and [C12mim]+ with a common bis(trifluoromethylsulfonyl)imide ([NTf2]−) anion. Extended Langmuir model fits to surface tension data are broadly consistent with those to RAS-LIF; however, several other common approaches to extracting surface compositions from measured surface tensions result in much larger discrepancies. MD simulations suggest that RAS-LIF faithfully reports on the alkyl-chain exposure at the surface, which is only subtly modified by composition-dependent structural reorganisation. more...

A novel scaffold for the construction of self-organised ionic liquids and ionic liquid crystals bearing both perfluorocarbon and hydrocarbon moieties has been developed. The phase behaviour and physical properties of these materials can be tuned as a function of chain length and fluorine content and significant structural elaboration is possible, giving a highly flexible system. more...

Small-angle neutron scattering experiments, supported by molecular dynamics simulations, have been performed on a range of compositions of the [C2mim]1−x[C12mim]x[Tf2N] ionic liquid mixture system. Isotopic contrast variation, through selective deuteration of both cations, has been used to assist in fitting the data to different scattering models. These data, and subsequent fitting, show that the structure of the ionic liquid mixtures changes substantially as a function of composition. Mixtures where x < 0.32 are dominated by aggregates of amphiphilic [C12mim]+ ions in the relatively polar [C2mim][Tf2N] solvent. Compositions where x > 0.32 can be described as bicontinuous, containing networks of both polar and non-polar domains, where the C12 chains of the [C12mim]+ ions percolate through the system to form a continuous non-polar sub-phase. Temperature-dependent scattering experiments suggest that there is relatively little change in bulk structure in these liquids between 20 and 60 °C. The presence of water, however, does influence some aspects of the liquid structure in a composition that is rich in [C2mim][Tf2N] (where x = 0.24). more...

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ispartof: FARADAY DISCUSSIONS vol:220 issue:0 pages:464-488 ispartof: location:England status: published

The liquid–vacuum interfaces of a series of ionic liquids (ILs) containing 1-alkyl-1-methylpyrrolidinium ([Cnmpyrr]+) cations of different alkyl chain lengths have been studied by reactive-atom scattering with laser-induced fluorescence detection (RAS-LIF) and molecular dynamics (MD) simulations. A direct, quantitative comparison has been performed between [Cnmpyrr]+ and the previously better-characterized 1-alkyl-3-methylimidazolium ([Cnmim]+) ILs with the same chain lengths, n, and common anion, bis(trifluoromethylsulfonyl)imide ([Tf2N]−). Both RAS-LIF experiments, using O(3P) as the projectile and monitoring OH yield, and MD simulations indicate that the coverage of the surface by alkyl chains is almost independent of the identity of the cation headgroup. Moreover, the potentially abstractable H atoms of the saturated pyrrolidinium ring do not contribute appreciably to the experimental OH yield. In both these senses, therefore, the headgroup is “hidden” from the probe particles approaching from vacuum.... more...

Two complementary approaches were used to study the liquid–vacuum interface of the liquid-crystalline ionic liquid 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C12mim][BF4]) in the smectic A (SmA) and isotropic phases. O atoms with two distinct incident translational energies were scattered from the surface of [C12mim][BF4]. Angle-dependent time-of-flight distributions and OH yields, respectively, were recorded from high- and low-energy O atoms. There were no significant changes in the measurements using either approach, nor the properties derived from them, accompanying the transition from the SmA to the isotropic phase. This indicates that the surface structure of [C12mim][BF4] remains essentially unchanged across the phase boundary, implying that the bulk order and surface structure are not strongly correlated for this material. This effect is ascribed to the strong propensity for the outer surfaces of ionic liquids to be dominated by alkyl chains, over an underlying layer rich in anions and catio... more...

The synthesis, liquid crystal and conductivity properties of a series of 27 salts based on the 5-(4-(alkyloxy)phenyl)-1,2,4-triazol-4-ium cation bearing a perfluoroalkyl chain with triflate, tetrafluoroborate and bistriflimide anion are reported. The cations are regarded as triphilic on account of their three distinct regions – hydrocarbon, fluorocarbon and ionic. The mesophases were characterised by a combination of polarised optical microscopy, calorimetry and small-angle scattering experiments using both X-rays and neutrons, while thermal stability was probed using thermogravimetric analysis. The liquid crystal properties are found to be dependent on the anion and the length of the perfluorocarbon chain, which effects combine to determine aspects of the self-organisation in the mesophases. A strong dependence of conductivity on the anion is seen, which is in turn related to its charge density. more...

The atomic-level description of liquid interfaces has lagged behind that of solid crystalline surfaces because existing experimental techniques have been limited in their capability to report molecular structure in a fluctuating liquid interfacial layer. We have moved toward a more detailed experimental description of the gas–liquid interface by studying the F-atom scattering dynamics on a common ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. When given contrast by deuterium labeling, the yield and dynamical behavior of reactively scattered HF isotopologues can resolve distinct signatures from the cation butyl, methyl, and ring groups, which help to quantify the relative populations of cation conformations at the liquid–vacuum interface. These results demonstrate the importance of molecular organization in driving site-specific reactions at the extreme outer regions of the gas–liquid interface. more...

The chemistry of phosphorus(III) ligands, which are of key importance in coordination chemistry, organometallic chemistry and catalysis, is dominated by relatively electron-rich species. Many of the electron-poor P(III) ligands that are readily available have relatively small steric profiles. As such, there is a significant gap in “ligand space” where more sterically bulky, electron-poor P(III) ligands are needed. This contribution discusses the coordination chemistry, steric and electronic properties of P(III) ligands bearing highly fluorinated alkoxide groups of the general form PRn(ORF)3-n, where R = Ph, RF = C(H)(CF3)2 and C(CF3)3; n = 1-3. These ligands are simple to synthesize and a range of experimental and theoretical methods suggest that their steric and electronic properties can be “tuned” by modification of their substituents, making them excellent candidates for large, electron-poor ligands. more...

A hydrogen bond of the type C-H⋅⋅⋅X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C-H⋅⋅⋅O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C-H⋅⋅⋅N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C-H⋅⋅⋅N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C-H⋅⋅⋅N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol-1 per hydrogen bond, which is similar to chemically and biologically relevant C-H⋅⋅⋅O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts. more...

The liquid–vacuum interfaces of a series of room-temperature ionic liquids (RTILs) containing the 1-alkyl-3-methylimidazolium cation ([Cnmim]) were investigated by reactive-atom scattering (RAS). The length of the alkyl chain (n = 4, 6, 8, and 12) and the anion type (bis(trifluoromethylsulfonyl)imide ([Tf2N]), trifluoromethanesulfonate ([OTf]), and tetrafluoroborate ([BF4])) were varied systematically to determine their effects on the preferential occupancy of the surface by alkyl chains. The experiments employed collisions with gas-phase, ground-state oxygen atoms, O(3P), generating OH and H2O products that revealed the abundance of abstractable H atoms at the liquid surface. Two complementary approaches with different O atom energies and detection methods were employed: we denote these RAS-laser-induced fluorescence (RAS-LIF) and RAS-mass spectrometry (RAS-MS). [Cnmim][BF4] RTILs were studied by both methods, giving consistent trends of strongly increasing alkyl coverage with chain length. Even for the ... more...

C-modified 7-deazaadenosines containing a diphenylacetylene moiety have been synthesised using cross-coupling approaches. The C-modified nucleosides exhibit remarkable fluorescence properties, including high quantum yields. Solvatochromic studies show a near linear correlation between the Stokes shift and solvent polarity which is indicative of intramolecular charge transfer. DFT calculations have allowed us to correlate the experimentally observed photophysical properties with the calculated HOMO-LUMO energy gaps within a series of real and model compounds. more...

A range of thio- and seleno-phosphonium cationic complexes [RE(PR'3)](+)[X](-) (R = Me, Ph; E = S, Se; X = GaCl4, SbF6) have been synthesised and structurally characterised. Reaction of [PhSPPh3][GaCl4] and [PhSePPh3][GaCl4] with P(t)Bu3 results in the ready transfer of the "RS(+)" and "RSe(+)" fragments from PPh3 to the stronger electron donor P(t)Bu3. NMR experiments combined with an Eyring analysis on the corresponding degenerate phosphine exchange reaction allowed the thermodynamic values for the phosphine exchange reaction of the sulfur cation (ΔH(‡) 18.7 ± 12.0 kJ mol(-1); ΔS(‡) -99.3 ± 36.3 J mol(-1) K(-1)) to be compared with the corresponding values (ΔH(‡) 2.4 ± 1.1 kJ mol(-1) and ΔS(‡) -58.1 ± 5.0 J mol(-1) K(-1)) for the [PhSePPh3](+) system. Importantly, the large negative entropy of activation and linear dependence on the rate of exchange are compatible with an SN2-type exchange process. This conclusion is supported by DFT calculations which confirm that the phosphine exchange process occurs via an associative mechanism. The rate of exchange was found to increase from sulfur to selenium and those with aryl substituents underwent exchange faster than those with alkyl substituents. more...

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Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than by synthesizing a large array of pure ILs with different chemical structures. In addition, these mixtures can exhibit a range of properties and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control of IL properties for particular applications. However, the fundamental properties, structure, and dynamics of IL mixtures are currently poorly understood, which limits their more widespread application. This article presents the first comprehensive investigation into the bulk and surface properties of IL mixtures formed from two commonly encountered ILs: 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C more...

The scope of the univalent gallium salts [Ga(C6H5F)2]+[Al(ORF)4]− and the new completely characterized [Ga(1,3,5-Me3C6H3)2]+[Al(ORF)4]− (RF = C(CF3)3) was investigated in terms of initiating or catalyzing the synthesis of highly reactive poly(2-methylpropylene)—highly reactive polyisobutylene (HR-PIB)—in several solvents. A series of polymerization reactions proved the high efficiency and quality of the univalent gallium salts for the polymerization of isobutylene. The best results were obtained using very low concentrations of [Ga(C6H5F)2]+[Al(ORF)4]− (down to 0.007 mol%) while working at reaction temperatures of up to ±0 °C and in the noncarcinogenic and non-water hazardous solvent toluene. Under these conditions, HR-PIB with an α-content of terminal olefinic double bonds up to 91 mol% and a molecular weight of 1000–2000 was obtained in good yields. Upon changing [Ga(C6H5F)2]+[Al(ORF)4]− for the electron richer [Ga(1,3,5-Me3C6H3)2]+[Al(ORF)4]−, polymerization temperatures could be increased to +10 °C. T... more...

The facile synthesis of a stable and isolable compound with a fluoroalkynyl group, M−C≡CF, is reported. Reaction of [Ru(C≡CH)(η5-C5Me5)(dppe)] with an electrophilic fluorinating agent (NFSI) results in the formation of the fluorovinylidene complex [Ru(=C=CHF)(η5-C5Me5)(dppe)][N(SO2Ph)2]. Subsequent deprotonation with LiN(SiMe3)2 affords the fluoroalkynyl complex [Ru(C≡CF)(η5-C5Me5)(dppe)]. In marked contrast to the rare and highly reactive examples of fluoroalkynes that have been reported previously, this compound can be readily isolated and structurally characterized. This has allowed the structure and bonding in the CCF motif to be explored. Further electrophilic fluorination of this species yields the difluorovinylidene complex [Ru(C=CF2)(η5-C5Me5)(dppe)][N(SO2Ph)2]. more...

The sensitivity of ionic liquids (ILs) to water affects their physical and chemical properties, even at relatively low concentrations, yet the structural thermodynamics of protic IL– (PIL−) water systems at low water concentrations still remains unclear. Using the rigorous Kirkwood–Buff theory of solutions, which can quantify the interactions between species in IL–water systems solely from thermodynamic data, we have shown the following: (1) Between analogous protic and aprotic ILs (AILs), the AIL cholinium bis(trifluoromethanesulfonyl)imide ([Ch][NTf2]) shows stronger interactions with water at low water concentrations, with the analogous PIL N,N-dimethylethanolammonium bis(trifluoromethanesulfonyl)imide ([DMEtA][NTf2]) having stronger water–ion interactions at higher water contents, despite water–ion interactions weakening with increasing water content in both systems. (2) Water has little effect on the average ion–ion interactions in both protic and aprotic ILs, aside from the AIL [Ch][NTf2], which sho... more...

Two complementary approaches were used to study the liquid-vacuum interface of the liquid-crystalline ionic liquid 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C

ion of a Cl(-) ion from the P-chlorophospholes, R4C4PCl (R=Me, Et), produced the P--P bonded cations [R4C4P--P(Cl)C4R4]+, which reacted with PPh3 to afford X-ray crystallographically characterised phosphine-phosphenium cations [R4C4P(PPh3)]+ (R=Me, Et). Examination of the 31P-{1H} NMR spectrum of a solution (CH2Cl(2)) of [Et4C4P-(PPh3)]+ and PPh3 revealed broadening of the resonances due to both free and coordinated PPh3, and importantly it proved possible to measure the rate of exchange between PPh3 and [Et4C4P-(PPh3)]+ by line shape analysis (gNMR programmes). The results established second-order kinetics with DeltaS( not equal)=(-106.3+/-6.7) J mol(-1) K(-1), DeltaH( not equal)=(14.9+/-1.6) kJ mol(-1) and DeltaG( not equal) (298.15 K)=(46.6+/-2.6) kJ mol(-1), values consistent with a SN2-type pathway for the exchange process. This result contrasts with the dominant dissociative (S(N)1-type) pathway reported for the analogous exchange reactions of the [ArNCH2CH2N(Ar)P(PMe3)]+ ion, and to understand in more detail the factors controlling these two different reaction pathways, we have analysed the potential energy surfaces using density functional theory (DFT). The calculations reveal that, whilst phosphine exchange in [Et4C4P(PPh3)]+ and [ArNCH2CH2N(Ar)P(PMe3)](+) is superficially similar, the two cations differ significantly in both their electronic and steric requirements. The high electrophilicity of the phosphorus center in [Et4C4P]+, combined with strong pi-pi interactions between the ring and the incoming and outgoing phenyl groups of PPh3, favours the SN2-type over the SN1-type pathway in [Et4C4P(PPh3)]+. Effective pi-donation from the amide groups reduces the intrinsic electrophilicity of [ArNCH2CH2N(Ar)P]+, which, when combined with the steric bulk of the aryl groups, shifts the mechanism in favour of a dissociative SN1-type pathway. more...

Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels–Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic. more...

Deprotonation of the 1-isopropyl-3-(phenylamino)pyridin-1-ium iodide gives the corresponding neutral betaine, which is formalised as a pyridinium-amido ligand when coordinated to a metal. Spectroscopic, structural and theoretical methods have been used to investigate the metal-ligand bonding, ligand dynamics and electron distribution. Collectively, the data show that the ligand can be characterised as a pseudo-amide and is a strong donor akin to alkyl phosphines and N-heterocyclic carbenes. Furthermore, rotation about both N substituent C-N bonds occurs, which is in contrast to the two alternative pyridinium positional isomers that exhibit neutral resonance structures. For comparison, compounds and complexes derived from norharman were prepared, which contain an additional C-C bond supporting conjugation and the accessibility of a neutral resonance structure. Notwithstanding the formal neutral structure, norharman-derived ligands are comparably strong donors, and have the additional advantage of exhibiting stability to dioxygen and water. more...

The fluoride ion affinities (FIAs) of 33 phosphenium ions with a range of substituents were calculated using ab inito and DFT methods. The use of these FIA data as a measure of the Lewis acidities of phosphenium ions is described and the FIAs of the species studied here are compared to FIA data for more commonly encountered Lewis acids. Phosphenium ions are often stronger Lewis acids than neutral species, but in many cases are less Lewis acidic than highly electrophilic cations such as [Me(3)C](+) or [Me(3)Si](+). The impact of mesomeric, inductive and steric substituent effects on FIAs are discussed and related to the underlying electronic structures of different cation types. A comparison between the FIAs of known "free" phosphenium ions with those that are currently unknown and other highly electrophilic cations suggests that some diaryl- and dialkylphosphenium ions may yet be accessible under the right conditions. more...

IR spectroscopic and X-ray structural data of rhodium and palladium complexes of N-heterocyclic carbene (NHC) and 1H-pyridin-(2E)-ylidene (PYE) ligands indicate that both ligand classes exhibit similar electron-donating properties. However, catalytic application of palladium PYE complexes appears to be limited by PYE ligand loss. Density functional theory (DFT) calculations show that the Pd–CNHC σ-bond is very low-lying in energy (HOMO-14 and 15, ca. –11 eV) and a π-backbonding contribution is also present, whereas the Pd-NPYE σ-bond is comparatively high-lying (HOMO-9 and 10, ca. –8 eV) and the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap is also significantly less (4.0 vs. 5.6 eV). Essentially, electronegativity differences between Pd, C, and N render the Pd–N bond much more polarized and susceptible to electrophilic and nucleophilic attack and hence ligand substitution. more...

The reactivity of photolytically generated, gas-phase, ground-state atomic oxygen, O(3P), with the surfaces of a series of 1-alkyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide ([NTf2]) ionic liquids has been investigated. The liquids differ only in the length of the linear CnH2n+1 alkyl side chain on the cation, with n = 2, 4, 5, 8, and 12. Laser-induced fluorescence was used to detect gas-phase OH v′ = 0 radicals formed at the gas-liquid interface. The reactivity of the ionic liquids increases nonlinearly with n, in a way that cannot simply be explained by stoichiometry. We infer that the alkyl chains must be preferentially exposed at the interface to a degree that is dependent on chain length. A relatively sharp onset of surface segregation is apparent in the region of n = 4. The surface specificity of the method is confirmed through the nonthermal characteristics of both the translational and rotational distributions of the OH v′ = 0. These reveal that the dynamics are dominated by a direct, impulsive scattering mechanism at the outer layers of the liquid. The OH v′ = 0 yield is effectively independent of the bulk temperature of the longest-chain ionic liquid in the range 298-343 K, also consistent with a predominantly direct mechanism. These product attributes are broadly similar to those of the benchmark pure hydrocarbon liquid, squalane, but a more detailed analysis suggests that the interface may be microscopically smoother for the ionic liquids. © 2010 American Chemical Society. more...

Collisions of hyperthermal oxygen atoms, with an average laboratory-frame translational energy of 520 kJ mol−1, on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf2]) and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C12mim][NTf2]), were studied with the use of a beam-surface scattering technique. Time-of-flight and angular distributions of inelastically scattered O and reactively scattered OH and H2O were collected for various angles of incidence with the use of a rotatable mass spectrometer detector. For both O and OH, two distinct scattering processes were identified, which can be empirically categorized as thermal and nonthermal. Nonthermal scattering is more probable for both O and OH products. The observation of OH confirms that at least some reactive sites, presumably alkyl groups, must be exposed at the surface. The ionic liquid with the longer alkyl chain, [C12mim][NTf2], is substantially more reactive than the l... more...

A novel metal-induced template for the self-assembly of two independent phosphane ligands by means of unprecedented multiple noncovalent interactions (classical hydrogen bond, weak hydrogen bond, metal coordination, pi-stacking interaction) was developed and investigated. Our results address the importance and capability of weak hydrogen bonds (WHBs) as important attractive interactions in self-assembling processes based on molecular recognition. Together with a classical hydrogen bond, WHBs may serve as promoters for the specific self-assembly of complementary monomeric phosphane ligands into supramolecular hybrid structures. The formation of an intermolecular C-H...N hydrogen bond and its persistence in the solid state and in solution was studied by X-ray crystal analysis, mass spectrometry and NMR spectroscopy analysis. Further evidence was demonstrated by DFT calculations, which gave specific geometric parameters for the proposed conformations and allowed us to estimate the energy involved in the hydrogen bonds that are responsible for the molecular recognition process. The presented template can be regarded as a new type of self-assembled beta-turn mimic or supramolecular pseudo amino acid for the nucleation of beta-sheet structures when attached to oligopeptides. more...

We present a fast and reliable general estimation of the heat capacity, Cp, and temperature-dependent density, ρ, of ionic liquids, based on a new in silico method to calculate the molecular volume, Vm. The knowledge of Vm allows the prediction of many physical properties of hitherto unknown ionic liquids as well as the prediction of lattice energies and entropies of salts. more...

The principles of protein structure design, molecular recognition, and supramolecular and combinatorial chemistry have been applied to develop a convergent metal-ion-assisted self-assembly approach that is a very simple and effective method for the de novo design and the construction of topologically predetermined antiparallel beta-sheet structures and self-assembled catalysts. A new concept of in situ generation of bidentate P-ligands for transition-metal catalysis, in which two complementary, monodentate, peptide-based ligands are brought together by employing peptide secondary structure motif as constructing tool to direct the self-assembly process, is achieved through formation of stable beta-sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by (1)H, (31)P, and (13)C NMR spectroscopy, ESI mass spectrometry, X-ray structure analysis, and theoretical calculations. Our initial catalysis results confirm the close relationship between the self-assembled sheet conformations and the catalytic activity of these metallopeptides in the asymmetric rhodium-catalyzed hydroformylation. Good catalyst activity and moderate enantioselectivity were observed for the selected combination of catalyst and substrate, but most importantly the concept of this new methodology was successfully proven. This work presents a perspective interface between protein design and supramolecular catalysis for the design of beta-sheet mimetics and screening of libraries of self-organizing supramolecular catalysts. more...

The use of supercritical carbon dioxide (scCO2) to extract valuable lipophilic compounds from miscanthus was investigated and subsequent enzymatic saccharification was carried out to determine the impact of scCO2 extraction on downstream processing of miscanthus. Two miscanthus genotypes (Miscanthus x. giganteus and Miscanthus sinensis) were investigated and characterized. A diverse range of molecules were detected including long-chain hydrocarbons, fatty acids, n-policosanols, aldehydes, wax esters, sterols and steroid ketones. Quantification data indicates that there is a considerable difference among each species in the quantities of specific compounds. The waxes also exhibited significant differences in melting temperature, thus illustrating the opportunity for utilization in various applications. In addition to the isolation of valuable chemical compounds, the scCO2 pretreatment also had a beneficial effect on the downstream processing of the biomass. The total sugars released after saccharification was found to increase by around 20% when coupled with scCO2 extraction, as compared to untreated samples. more...

Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes. more...