Hydrogen Bonding with Hydridic Hydrogen-Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?

Spectroscopic characteristics of Me3Si-H···Y complexes (Y = ICF3, BrCN, and HCN) containing a hydridic hydrogen were determined experimentally by low-temperature IR experiments based on the direct spectral measurement of supersonically expanded intermediates on a cold substrate or by the technique of argon-matrix isolation as well as computationally at harmonic and one-dimensional anharmonic levels. The computations were based on DFT-D, MP2, MP2-F12, and CCSD(T)-F12 levels using various extended AO basis sets. The formation of all complexes related to the redshift of the Si-H stretching frequency upon complex formation was accompanied by an increase in its intensity. Similar results were obtained for another 10 electron acceptors of different types, positive σ-, π-, and p-holes and cations. The formation of HBe-H···Y complexes, studied only computationally and again containing a hydridic hydrogen, was characterized by the blueshift of the Be-H stretching frequency upon complexation accompanied by an increase in its intensity. The spectral shifts and stabilization energies obtained for all presently studied hydridic H-bonded complexes were comparable to those in protonic H-bonded complexes, which has prompted us to propose a modification of the existing IUPAC definition of H-bonding that covers, besides the classical protonic form, the non-classical hydridic and dihydrogen forms.

Selected ion flow tube mass spectrometry analyses of isobaric compounds methanol and hydrazine in humid air.

RATIONALE: The volatile compounds generated by the electrochemical reduction of atmospheric carbon dioxide and nitrogen include isobaric methanol (CH3 OH) and, potentially, hydrazine (N2 H4 ). To achieve quantification of hydrazine molecules by selected ion flow tube mass spectrometry (SIFT-MS), its reactions with H3 O+ , NO+ and O2 + reagent ions must be understood. METHODS: A SIFT study (using a SIFT-MS instrument) was carried out to obtain rate coefficients and product ions for the reactions of H3 O+ , NO+ and O2 + reagent ions with N2 H4 and CH3 OH molecules present in the humid headspace of their aqueous solutions. Using the kinetics data obtained, solution headspace concentrations were determined for both compounds as a function of their liquid-phase concentrations at 10, 20 and 35°C. RESULTS: Both compounds react with H3 O+ ions via rapid proton transfer to produce CH3 OH2 + and H5 N2 + ions with the common m/z value of 33. It is revealed that NO+ rapidly transfers charge to N2 H4 (rate coefficient k = 2.3 × 10-9 cm3 s-1 ) but only slowly associates with CH3 OH (k2eff = 7.1 × 10-11 cm3 s-1 ). Thus, selective analysis can be achieved using both H3 O+ and NO+ reagent ions. The headspace methanol vapour concentration was found to increase with increasing solution temperature, but that of hydrazine decreased with an associated increase of ammonia (NH3 ) as measured with O2 + reagent ions. CONCLUSIONS: The isobaric compounds methanol and hydrazine can be separately analysed in real time by SIFT-MS using H3 O+ and NO+ reagent ions, even when they co-occur in humid air. The evolution of hydrazine from aqueous solutions can be quantitatively monitored together with its decomposition at elevated temperatures.

The development of a fully integrated 3D printed electrochemical platform and its application to investigate the chemical reaction between carbon dioxide and hydrazine.

The combination of computer assisted design and 3D printing has recently enabled fast and inexpensive manufacture of customized 'reactionware' for broad range of electrochemical applications. In this work bi-material fused deposition modeling 3D printing is utilized to construct an integrated platform based on a polyamide electrochemical cell and electrodes manufactured from a polylactic acid-carbon nanotube conductive composite. The cell contains separated compartments for the reference and counter electrode and enables reactants to be introduced and inspected under oxygen-free conditions. The developed platform was employed in a study investigating the electrochemical oxidation of aqueous hydrazine coupled to its bulk reaction with carbon dioxide. The analysis of cyclic voltammograms obtained in reaction mixtures with systematically varied composition confirmed that the reaction between hydrazine and carbon dioxide follows 1/1 stoichiometry and the corresponding equilibrium constant amounts to (2.8 ± 0.6) × 103. Experimental characteristics were verified by results of numerical simulations based on the finite-element-method.

Time-integrated thermal desorption for quantitative SIFT-MS analyses of atmospheric monoterpenes.

A new time-integrated thermal desorption technique has been developed that can be used with selected ion flow tube mass spectrometry, TI-TD/SIFT-MS, for off-line quantitative analyses of VOCs accumulated onto sorbents. Using a slow desorption temperature ramp, the absolute amounts of desorbed compounds can be quantified in real time by SIFT-MS and constitutional isomers can be separated. To facilitate application of this technique to environmental atmospheric monitoring, method parameters were optimised for quantification of the three common atmospheric monoterpenes: ß-pinene, R-limonene and 3-carene. Three sorbent types, Tenax TA, Tenax GR and Porapak Q, were tested under 26 different desorption conditions determined by the "design of experiment", DOE, systematic approach. The optimal combination of type of sorbent, bed length, sampling flow rate, sample volume and the initial desorption temperature was determined from the experimental results by ANOVA. It was found that Porapak Q exhibited better efficiency of sample collection and further extraction for total monoterpene concentration measurements. On the other hand, Tenax GR or TA enabled separation of all three monoterpenes. The results of this laboratory study were tested with the sample accumulated from a branch of a Pinus nigra tree. Graphical abstract.

Evaluation of lipid peroxidation by the analysis of volatile aldehydes in the headspace of synthetic membranes using Selected Ion Flow Tube Mass Spectrometry, SIFT-MS.

RATIONALE: Oxidative stress of cell membranes leads to a number of pathological processes associated with some diseases and is accompanied by the release of volatile aldehydes, which, potentially, can be used as biomarkers. Thus, the aim was to investigate peroxidation of defined synthetic membranes by direct quantitative analysis of volatile aldehydes. METHODS: The concentration spectra of volatile compounds present in the headspace of synthetic membranes under peroxidation stress and following mechanical stress due to sonication were obtained using solid phase microextraction (SPME) in combination with Gas Chromatography Mass Spectrometry (SPME/GC/MS) and Selected Ion Flow Tube Mass Spectrometry (SIFT-MS). The focus was on the direct, real time quantification of volatile aldehydes. In addition, the total aldehydes in the aqueous membrane suspensions were quantified using the TBARS method. RESULTS: Propanal, butanal, pentanal, hexanal, heptanal and malondialdehyde were detected and quantified in the humid headspace of the media containing the synthetic membranes following peroxidation. The composition and concentration of these saturated aldehydes strongly depend on the unsaturated fatty acids representation in the liposomes. Some protective effect of cholesterol was observed especially for membranes peroxidised by Fenton reagents and after application of a mechanical stress. CONCLUSIONS: This study demonstrates that peroxidation of model synthetic membranes in vitro can be tracked in real time using direct quantification by SIFT-MS of several specific aldehydes in the headspace of the membrane suspensions. Cholesterol plays an important role in retaining membrane structure and can indirectly protect membranes from lipid peroxidation.

Direct detection and quantification of malondialdehyde vapour in humid air using selected ion flow tube mass spectrometry supported by gas chromatography/mass spectrometry.

RATIONALE: It has been proposed that malondialdehyde (MDA) reflects free oxygen-radical lipid peroxidation and can be useful as a biomarker to track this process. For the analysis of MDA molecules in humid air by selected ion flow tube mass spectrometry (SIFT-MS), the rate coefficients and the ion product distributions for the reactions of the SIFT-MS reagent ions with volatile MDA in the presence of water vapour are required. METHODS: The SIFT technique has been used to determine the rate coefficients and ion product distributions for the reactions of H3O(+), NO(+) and O2 (+•) with gas-phase MDA. In support of the SIFT-MS analysis of MDA, solid-phase microextraction, SPME, coupled with gas chromatography/mass spectrometry, GC/MS, has been used to confirm the identification of MDA. RESULTS: The primary product ions have been identified for the reactions of H3O(+), NO(+) and O2 (+•) with MDA and the formation of their hydrates formed in humid samples is described. The following combinations of reagent and the analyte ions (given as m/z values) have been adopted for SIFT-MS analyses of MDA in the gas phase: H3O(+): 109; NO(+): 89, 102; O2 (+•): 72, 90, 108, 126. The detection and quantification of MDA released by a cell culture by SIFT-MS are demonstrated. CONCLUSIONS: This detailed study has provided the kinetics data required for the SIFT-MS analysis of MDA in humid air, including exhaled breath and the headspace of liquid-phase biogenic media. The detection and quantification by SIFT-MS of MDA released by a cell culture are demonstrated.

Combining Fourier transform nuclear quadrupole resonance (FT-NQR) spectroscopy and mass spectrometry (MS) to study the electronic structure of titanocene dichlorides.

A combination of nuclear quadrupole resonance spectroscopy (NQR) and mass spectrometry (MS) has been used to observe trends in electronic structure in three titanocenes: bis(cyclopentadienyl) titanium dichloride (η(5)-C(5)H(5))(2)TiCl(2), bis(pentamethylcyclopentadienyl) titanium dichloride (η(5)-C(5)(CH(3))(5))(2)TiCl(2) and dimethylsilylene-bridged ansa bis(cyclopentadienyl) titanium dichloride Si(CH(3))(2)(η(5)-C(5)H(5))(2)TiCl(2). Using MS, electron ionisation mass spectra of these compounds are presented within the context of the entire homologous series with one to five methyl groups on each cyclopentadienyl ligand. A dedicated NQR spectrometer was constructed for this study with a sensitivity sufficient to precisely determine the NQR resonant frequency of (35)Cl atoms using 3 g samples of these titanocenes. The observed frequencies are thus 11.784, 11.930 and 10.863 MHz at 298 K. The results demonstrate that NQR using a relatively simple apparatus can be used as a sensitive and cost effective probe into the molecular structure of organometallic chlorides, which complements the information inferred from the mass spectra.

Hydrogenation of titanocene and zirconocene bis(trimethylsilyl)acetylene complexes.

Reactions following the addition of dihydrogen under maximum atmospheric pressure to bis(trimethylsilyl)acetylene (BTMSA) complexes of titanocenes, [(η5-C5H5-nMen)2Ti(η2-BTMSA)] (n = 0, 1, 3, and 4) (1A-1D), and zirconocenes, [(η5-C5H5-nMen)2Zr(η2-BTMSA)] (n = 2-5) (4A-4D), proceeded in diverse ways and, depending on the metal, afforded different products. The former complexes lost, in all cases, their BTMSA ligand via its hydrogenation to bis-1,2-(trimethylsilyl)ethane when reacted at 80 °C for a prolonged reaction time. For n = 0, 1, and 3, the titanocene species formed in situ dimerised via the formation of fulvalene ligands and two bridging hydride ligands, giving known green dimeric titanocenes (2A-2C). For n = 4, a titanocene hydride [(η5-C5HMe4)2TiH] (2D) was formed, similarly to the known [(η5-C5Me5)2TiH] (2E) for n = 5; however, in contrast to this example, 2D in the absence of dihydrogen spontaneously dehydrogenated to the known Ti(iii)-Ti(iii) dehydro-dimer [{Ti(η5-C5HMe4)(µ-η1:η5-C5Me4)}2] (3B). This complex has now been fully characterised via spectroscopic methods, and was shown through EPR spectroscopy to attain an intramolecular electronic triplet state. The zirconocene-BTMSA complexes 4A-4D reacted uniformly with one hydrogen molecule to give Zr(iv) zirconocene hydride alkenyls, [(η5-C5H5-nMen)2ZrH{C(SiMe3)[double bond, length as m-dash]CH(SiMe3)}] (n = 2-5) (5A-5D). These were identified through their 1H and 13C NMR spectra, which show features typical of an agostically bonded proton, [double bond, length as m-dash]CH(SiMe3). Compounds 5A-5D formed equilibria with the BTMSA complexes 4A-4D depending on hydrogen pressure and temperature.

Decamethyltitanocene hydride intermediates in the hydrogenation of the corresponding titanocene-(η2-ethene) or (η2-alkyne) complexes and the effects of bulkier auxiliary ligands.

1H NMR studies of reactions of titanocene [Cp*2Ti] (Cp* = η5-C5Me5) and its derivatives [Cp*(η5:η1-C5Me4CH2)TiMe] and [Cp*2Ti(η2-CH2[double bond, length as m-dash]CH2)] with excess dihydrogen at room temperature and pressures lower than 1 bar revealed the formation of dihydride [Cp*2TiH2] (1) and the concurrent liberation of either methane or ethane, depending on the organometallic reactant. The subsequent slow decay of 1 yielding [Cp*2TiH] (2) was mediated by titanocene formed in situ and controlled by hydrogen pressure. The crystalline products obtained by evaporating a hexane solution of fresh [Cp*2Ti] in the presence of hydrogen contained crystals having either two independent molecules of 1 in the asymmetric part of the unit cell or cocrystals consisting of 1 and [Cp*2Ti] in a 2 : 1 ratio. Hydrogenation of alkyne complexes [Cp*2Ti(η2-R1C[triple bond, length as m-dash]CR2)] (R1 = R2 = Me or Et) performed at room temperature afforded alkanes R1CH2CH2R2, and after removing hydrogen, 2 was formed in quantitative yields. For alkyne complexes containing bulkier substituent(s) R1 = Me or Ph, R2 = SiMe3, and R1 = R2 = Ph or SiMe3, successful hydrogenation required the application of increased temperatures (70-80 °C) and prolonged reaction times, in particular for bis(trimethylsilyl)acetylene. Under these conditions, no transient 1 was detected during the formation of 2. The bulkier auxiliary ligands η5-C5Me4tBu and η5-C5Me4SiMe3 did not hinder the addition of dihydrogen to the corresponding titanocenes [(η5-C5Me4tBu)2Ti] and [(η5-C5Me4SiMe3)2Ti] yielding [(η5-C5Me4tBu)2TiH2] (3) and [(η5-C5Me4SiMe3)2TiH2] (4), respectively. In contrast to 1, the dihydride 4 did not decay with the formation of titanocene monohydride, but dissociated to titanocene upon dihydrogen removal. The monohydrides [(η5-C5Me4tBu)2TiH] (5) and [(η5-C5Me4SiMe3)2TiH] (6) were obtained by insertion of dihydrogen into the intramolecular titanium-methylene σ-bond in compounds [(η5-C5Me4tBu)(η5:η1-C5Me4CMe2CH2)Ti] and [(η5-C5Me4SiMe3)(η5:η1-C5Me4SiMe2CH2)Ti], respectively. The steric influence of the auxiliary ligands became clear from the nature of the products obtained by reacting 5 and 6 with butadiene. They appeared to be the exclusively σ-bonded η1-but-2-enyl titanocenes (7) and (8), instead of the common π-bonded derivatives formed for the sterically less congested titanocenes, including [Cp*2Ti(η3-(1-methylallyl))] (9). The molecular structure optimized by DFT for compound 1 acquired a distinctly lower total energy than the analogously optimized complex with a coordinated dihydrogen [Cp*2Ti(η2-H2)]. The stabilization energies of binding the hydride ligands to the bent titanocenes were estimated from counterpoise computations; they showed a decrease in the order 1 (-132.70 kJ mol-1), 3 (-121.11 kJ mol-1), and 4 (-112.35 kJ mol-1), in accordance with the more facile dihydrogen dissociation.

Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to-allene rearrangement, and the electronic transition relevant to the back-bonding interaction.

The titanocene-ethene complex [Ti(II)(η(2)-C2H4)(η(5)-C5Me5)2] (1) with simple internal alkynes R(1)C≡CR(2) gives complexes [Ti(II)(η(2)-R(1)C≡CR(2))(η(5)-C5Me5)2] {R(1), R(2): Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R(1) = Me and R(2) = t-Bu or i-Pr afford allene complexes [Ti(II)(η(2)-CH2=C=CHR(2))(η(5)-C5Me5)2] (11) and (12), whereas for R(2) = Et a mixture of alkyne complex (13A) and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC≡CSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R(1), R(2): Me), not obtainable from 1, together with compounds 3­6 and 10 (R(1), R(2): Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3­9 display the longest-wavelength electronic absorption band in the range 670-940 nm due to the HOMO → LUMO transition. The assignment of the first excitation to be of predominantly a b2 → a1 transition was confirmed by DFT calculations. The calculated first excitation energies for 3­9 followed the order of hypsochromic shifts of the absorption band relative to 8 that were induced by acetylene substituents: Me > Ph ≫ SiMe3. Computational results have also affirmed the back-bonding nature in the alkyne-to-metal coordination.

Exhaled breath concentrations of acetic acid vapour in gastro-esophageal reflux disease.

The objective of this experimental study was to discover volatile metabolites present in exhaled breath that could be used as biomarkers of gastro-esophageal reflux disease, GERD, one of the most common causes of chronic cough. An in vitro model based on pork tissue samples exposed to a challenge by artificial gastric fluid was used to identify specific volatile compounds to be chosen for quantification in directly exhaled breath of GERD patients and controls using selected ion flow tube mass spectrometry, SIFT-MS. GC/MS analyses of the headspace of this in vitro model indicated that the only volatile compound significantly increased was acetic acid. End expiratory concentration of acetic acid measured by SIFT-MS in mouth exhaled breath of 22 GERD patients (median 85 ppbv) was found to be significantly higher than that in breath of a control group (median 48 ppbv). Breath acetic acid may be useful for non-invasive diagnostics of GERD and other conditions resulting in the lowering of pH of the lining of the airways.

Synthetic transformations of a pendant nitrile moiety in group 4 metallocene complexes.

Functional group transformations at the group 4 metallocene framework have been demonstrated, which have provided relatively straightforward access to otherwise synthetically challenging derivatives. The pendant nitrile group in Ti and Zr metallocene complexes of the type [(η(5)-C5Me5)(η(5)-C5H4CMe2CH2CN)MCl2] was converted into an intramolecularly bound ketimido moiety by alkylation, which took place not only at the nitrile, but also at the metal centre. The choice of an alkylating reagent (alkyl/aryl lithium, Grignard reagent) was crucial: e.g., 2 equiv. of MeMgBr effected the alkylation only at the metal, yielding selectively complexes [(η(5)-C5Me5)(η(5)-C5H4CMe2CH2CN)MMe2], while the use of PhMgBr, PhLi, or MeLi instead gave selectively the ketimido complexes. Organyl lithium reagents were, however, not compatible with the titanocene derivatives. The metal-bound ketimides were subsequently cleaved off by the reaction with HCl, which afforded metallocene dichlorides with a pendant imino group. These compounds were easily protonated again at the nitrogen atom to produce a cationic iminium moiety. Aqueous hydrolysis of the imine or its respective hydrochloride proved to be viable in the case of Zr and it finally afforded a pendant ketone group attached to the zirconocene framework.

Combined use of gas chromatography and selected ion flow tube mass spectrometry for absolute trace gas quantification.

The value of the gas chromatography (GC) and selected ion flow tube mass spectrometry (SIFT-MS) combination for the analysis of trace gases is demonstrated by the quantification of acetone in air samples using the three precursor ions available to SIFT-MS, viz. H3O+, NO+ and O2+, and by the separation of the isomers 1-propanol and 2-propanol, and their analysis using H3O+ precursor ions. It is shown that the GC/SIFT-MS combination allows for accurate trace gas quantification obviating the regular, time-consuming calibrations that are usually required for the more commonly used detectors of GC systems, and the positive identification of isomers in mixtures that is often challenging using SIFT-MS alone. Thus, the GC/SIFT-MS combination paves the way to more confident analyses of complex mixtures such as exhaled breath.

N-[(1E)-Amino[3-methyl-5-(4-methylphenyl)-4,5-dihydro-1H-pyrazol-1-yl]methylene]-1H-imidazole-1-carboxamide.

In the title compound, C(16)H(18)N(6)O, an N-carbonylimidazole derivative of pyrazoline-1-carboximidamide, the pi-electron density of the N atom in the 1-position on the pyrazoline ring is delocalized through the amidine moiety and the adjacent carbonyl group. The imidazole ring, though coplanar with the rest of the molecule, is deconjugated. The pyrazoline ring adopts a flat-envelope conformation, having the substituted phenyl ring oriented perpendicular to the mean plane of the heterocycle. Both of the two potential hydrogen-bond donors are involved in intramolecular hydrogen-bonding interactions.

[Mu-1kappa2O,O':2(eta5)-Cyclopentadienylcarboxylato][2(eta5)-diphenylphosphinocyclopentadienyl]bis[1,1(eta5)-tetramethylcyclopentadienyl]iron(II)titanium(III).

Reacting stoichiometric amounts of 1-(diphenylphosphino)ferrocenecarboxylic acid and [Ti(eta(5)-C(5)HMe(4))(2)(eta(2)-Me(3)SiC[triple-bond]CSiMe(3))] produced the title carboxylatotitanocene complex, [[mu-1kappa(2)O,O':2(eta(5))-C(5)H(4)CO(2)][2(eta(5))-C(5)H(4)P(C(6)H(5))(2)][1(eta(5))-C(5)H(CH(3))(4)](2)Fe(II)Ti(III)] or [FeTi(C(9)H(13))(2)(C(6)H(4)O(2))(C(17)H(14)P)]. The angle subtended by the Ti/O/O' plane, where O and O' are the donor atoms of the kappa(2)-carboxylate group, and the plane of the carboxyl-substituted ferrocene cyclopentadienyl is 24.93(6) degree.