Analyses, extensions and comparison of three experimental schemes for measuring ((n)J(CH)+D(CH))-couplings at natural abundance

Three types of experiments for measuring (n)J(CH) heteronuclear long-range coupling constants are examined and extended with state-of-the-art pulse sequence building-blocks: The use of a HMBC with corresponding reference-HSQC for accurate coupling determination is combined with the constant time technique and the conversion of antiphase magnetization into ZQ/DQ-coherences; CPMG-based LR-CAHSQC and BIRD(r,X)-HSQMBC experiments are examined in detail with respect to their coherence transfer properties; finally, the HSQC-TOCSY-IPAP experiment is introduced, a sequence derived from previously published alpha and beta selective HSQC-TOCSYs using a different spin state selection technique and a recently developed ZQ-suppression method. The experiments are characterized with their advantages and disadvantages and compared using strychnine and menthol as standard molecules.     

Variable angle NMR spectroscopy and its application to the measurement of residual chemical shift anisotropy

The successful measurement of anisotropic NMR parameters like residual dipolar couplings (RDCs), residual quadrupolar couplings (RQCs), or residual chemical shift anisotropy (RCSA) involves the partial alignment of solute molecules in an alignment medium. To avoid any influence of the change of environment from the isotropic to the anisotropic sample, the measurement of both datasets with a single sample is highly desirable. Here, we introduce the scaling of alignment for mechanically stretched polymer gels by varying the angle of the director of alignment relative to the static magnetic field, which we call variable angle NMR spectroscopy (VA-NMR). The technique is closely related to variable angle sample spinning NMR spectroscopy (VASS-NMR) of liquid crystalline samples, but due to the mechanical fixation of the director of alignment no sample spinning is necessary. Also, in contrast to VASS-NMR, VA-NMR works for the full range of sample inclinations between 0° and 90°. Isotropic spectra are obtained at the magic angle. As a demonstration of the approach we measure 13C-RCSA values for strychnine in a stretched PDMS/CDCl? gel and show their usefulness for assignment purposes. In this context special care has been taken with respect to the exact calibration of chemical shift data, for which three approaches have been derived and tested.     

Transverse magnetization transfer under planar mixing conditions in spin systems consisting of three coupled spins 1/2

Polarization transfer under planar mixing conditions is a widely used tool in modern NMR-experiments. In the case of two coupled spins 1/2 or a chain of three or more spins 1/2 with only nearest neighbor couplings, it is only possible to transfer a single magnetization component (longitudinal magnetization in the principle axis system of the planar coupling tensors). However, if all couplings in a three-spin system are non-zero, it turns out that all magnetization components can be efficiently transferred even under strictly planar mixing conditions. In this article a detailed theoretical analysis is presented based on analytical transverse coherence transfer functions and on the underlying commutator algebra. In addition, transverse magnetization transfer is demonstrated experimentally. The results show that in highly coupled spin systems, as for example in the case of partially aligned samples with many residual dipolar couplings, special care has to be taken to avoid phase distortions if planar mixing steps are used.     

Mechanistic Studies on the Gas‐Phase Dehydrogenation of Alkanes at Cyclometalated Platinum Complexes

In the ion/molecule reactions of the cyclometalated platinum complexes [Pt(L? H)]⁺ (L=2,2′‐bipyridine (bipy), 2‐phenylpyridine (phpy), and 7,8‐benzoquinoline (bq)) with linear and branched alkanes C_nH_2n+2 (n=2–4), the main reaction channels correspond to the eliminations of dihydrogen and the respective alkenes in varying ratios. For all three couples [Pt(L? H)]⁺/C₂H₆, loss of C₂H₄ dominates clearly over H₂ elimination; however, the mechanisms significantly differs for the reactions of the “rollover”‐cyclometalated bipy complex and the classically cyclometalated phpy and bq complexes. While double hydrogen‐atom transfer from C₂H₆ to [Pt(bipy? H)]⁺, followed by ring rotation, gives rise to the formation of [Pt(H)(bipy)]⁺, for the phpy and bq complexes [Pt(L? H)]⁺, the cyclometalated motif is conserved; rather, according to DFT calculations, formation of [Pt(L? H)(H₂)]⁺ as the ionic product accounts for C₂H₄ liberation. In the latter process, [Pt(L? H)(H₂)(C₂H₄)]⁺ (that carries H₂ trans to the nitrogen atom of the heterocyclic ligand) serves, according to DFT calculation, as a precursor from which, due to the electronic peculiarities of the cyclometalated ligand, C₂H₄ rather than H₂ is ejected. For both product‐ion types, [Pt(H)(bipy)]⁺ and [Pt(L? H)(H₂)]⁺ (L=phpy, bq), H₂ loss to close a catalytic dehydrogenation cycle is feasible. In the reactions of [Pt(bipy? H)]⁺ with the higher alkanes C_nH_2n+2 (n=3, 4), H₂ elimination dominates over alkene formation; most probably, this observation is a consequence of the generation of allyl complexes, such as [Pt(C₃H₅)(bipy)]⁺. In the reactions of [Pt(L? H)]⁺ (L=phpy, bq) with propane and n‐butane, the losses of the alkenes and dihydrogen are of comparable intensities. While in the reactions of “rollover”‐cyclometalated [Pt(bipy? H)]⁺ with C_nH_2n+2 (n=2–4) less than 15 % of the generated product ions are formed by C? C bond‐cleavage processes, this value is about 60 % for the reaction with neo‐pentane. The result that C? C bond cleavage gains in importance for this substrate is a consequence of the fact that 1,2‐elimination of two hydrogen atoms is no option; this observation may suggest that in the reactions with the smaller alkanes, 1,1‐ and 1,3‐elimination pathways are only of minor importance.     

The Reagent‐depending Nitration of 1,3‐Dihydroxyacetone Dimer

Two highly energetic nitric acid esters were synthesized from the dimer of dihydroxyacetone. 1,3‐Dinitratoacetone ( 1 ) and its dimer 2,5‐bis(nitratomethyl‐2,5‐nitrato)‐1,4‐dioxane ( 2 ) were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, and elemental analysis. The thermal behavior was investigated with DTA measurements. Although showing the same atomic stoichiometry, dimer 2 shows significantly higher sensitivities measured by BAM methods (drophammer and friction tester). Due to the high oxygen content of 62.2 %, 1 and 2 were evaluated as potential high energy dense oxidizers.     

A molecular modeling study of pentanol solubilized in a sodium octanoate micelle

In order to study the structural and dynamical aspects of the solubilization process of pentanol within a sodium octanoate micelle a molecular dynamics simulation is presented. In this initial study we discuss the results and detailed insights into the interactions between sodium octanoate, pentanol, and water. The total micellar radius and the hydrophobic core radius were determined. The calculated values are in fairly good agreement with experimental results. In contrast to pure sodium octanoate micelles the aggregate with dissolved pentanol attained a more spherical shape related to the time interval of the simulation. It is clear that the results of a molecular dynamics computer simulation are always limited by its total length and the total time used for data analysis. Nevertheless, from our simulation study it turned out that a part of the pentanol hydroxyl groups were located within the micellar core and some alcohol molecules were also observed at the surface region of the micelle. The corresponding partition coefficient was calculated and agreed well with the experiment. The evaluated radial distribution functions of the sodium ions, the octanoate oxygens, and the hydroxyl hydrogens reveal details of the interface region of the micelle and the bulk phase. Additionally, it was possible to calculate the trans-to-gauche ratios of the alkyl chains and to compare these results with the simulation of a pure octanoate micelle.