Investigation of the proton mobility in CsH(SO4)0.76(SeO4)0.24 crystal by H NMR spectroscopy

Crystals of CsH(SO₄)_0.76(SeO₄)_0.24 formulation were studied by ¹H NMR spectroscopy. The ¹H line-shape, the T₁ and T₂ relaxation times were determined as a function of temperature. The activation energies deduced from the temperature dependence of relaxation times were compared with the activation energy issued from conductivity measurements. The results obtained are discussed and supported by the Ngai model.     

Neutron powder diffraction, and solid-state deuterium NMR analyses of Yb2RuD6 and spectroscopic vibrational analysis of Yb2RuD6 and Yb2RuH6

The crystal structure of Yb₂RuD₆ has been determined by neutron powder diffraction and the results were consistent with the Fm3m (#225) space group, a=7.2352(18) Å, with the atoms arranged according to the well-known K₂PtCl₆ structure. No structural phase transition was observed in going from room temperature to 4 K. Raman spectra were not available due to fluorescence, but all fundamental bands and combination bands were assigned from FTIR and PAIR spectra only following previous studies for other alkaline earth and europium ruthenium ternary metal hydrides and deuterides. The deuterium nuclear quadrupole coupling constant, 40.9 kHz, leads to an ionic character of the Ru-D bond of 82%.     

Solid-state Na and C NMR characterization of Na3C60

Two separate samples of Na₃C₆₀ were prepared by direct reaction of C₆₀ with sodium metal vapor, and subjected to different annealing times of 10 days and 16 days. Solid-state ¹³C and ²³Na NMR, along with elemental analysis, powder X-ray diffraction (XRD) and Raman spectroscopy, were used to characterize both samples. The Raman spectra of both materials have a single peak at 1447 cm⁻¹ which correspond to the A_g peak of C₆₀³⁻, consistent with the stoichiometry of Na_xC₆₀ with x=3. The powder XRD patterns are also virtually identical for both samples. However, solid-state ²³Na and ¹³C NMR spectra of the two samples are significantly different, suggesting a relationship between annealing times and the final structure of the alkali fulleride. Variable-temperature ²³Na magic-angle spinning (MAS) NMR experiments reveal the existence of two or three distinct sodium species and reversible temperature-dependent diffusion of sodium ions between octahedral and tetrahedral interstitial sites. ¹³C MAS NMR experiments are used to identify resonances corresponding to free C₆₀ and fulleride species, implying that the samples are segregated-phase materials composed of C₆₀ and non-stoichiometric Na₃C₆₀. Variable-temperature ¹³C MAS NMR experiments reveal temperature-dependent motion of the fullerides.     

Solid-state Al NMR investigation of thermal decomposition of LiAlH4

Solid-state nuclear magnetic resonance is used to study the thermal decomposition of lithium tetrahydroaluminate into metallic aluminum, hydrogen and trilithium hexahydroaluminate. Aluminum sites in LiAlH₄ and Li₃AlH₆ were characterized using static, magic angle spinning (MAS) and multiple-quantum MAS NMR. By applying the in situ NMR method, it has been demonstrated that melting is not a prerequisite for the decomposition of LiAlH₄. Based on the observed data, a decomposition path has been established that is consistent with the concentrations of observed Al species at various stages of the thermally induced reaction.     

钒、铬、锰磷桥络合物中31P NMR化学位移的研究

ISSIe山和W6flSChllh山子1960年首次用pdCI。和二苯基磷合成出黄色的二聚络合物，后被H。yieY＊确认为具有pRZ的桥式结构．此后一系列该类结构的化合物被合成并引起了广泛的兴趣．磷可以和两个甚至多个金属原子络合构成多核金属络合物，在催化反应中有重要应用．磷原子存在多种电子态，其3d空轨道也能参与成键．P乃1的NMR谱是研究含磷化合物立体结构的有力工具．P－31与其它核素之间的耦合常数以及P－31的化学位移对阐明化合物的立体构象以及电子结构具有重要作用．近年来，West饲用计算机神经网络技术预测P－：if的化学位移，但仅…     

1H mas NMR study of OH groups in the AlPO4/SiO2 system

Three solids of composition SiO₂, AlPO₄ and 20∶80 mol/mol AlPO₄/SiO₂, respectively, were synthesized. Their textural properties were examined and¹H MAS NMR spectroscopy was used to characterize their surface OH groups. The results reveal that the solids are amorphous and texturally suitable for use as catalysts.     

129Xe NMR study of the localization of PdCl2 supported on carbon nanotubes

Localization of PdCl₂ clusters supported on multi-wall carbon nanotubes (MWCNT) has been investigated using ¹²⁹Xe NMR of adsorbed xenon. As-made MWCNTs with channels initially inaccessible for adsorption and ball-milled MWCNTs with the totally accessible internal surface were used as supports. The observed ¹²⁹Xe NMR spectra were determined by the dynamics of xenon exchange between the aggregate pores and nanotube channels. No considerable changes of the ¹²⁹Xe NMR spectrum with the concentration of supported PdCl₂ were observed for the as-made MWCNT, while an additional resonance appeared for the ball-milled nanotubes. The ¹²⁹Xe NMR experiments evidenced the supported species to be localized on the internal surface of the ball-milled MWCNT.     

Dynamics of [Zn(D2O)6] in [Zn(D2O)6][SiF6] crystal as studied by 1D, 2D spectra and spin-lattice relaxation time of H NMR

The dynamics of [Zn(D₂O)₆]²⁺ in [Zn(D₂O)₆][SiF₆] was investigated by ²H NMR one-dimensional spectra, two-dimensional exchange spectra and spin-lattice relaxation time (T₁). The lineshapes of those spectra and T₁ were dominated by the 180° flip of the water molecules and the reorientation of [Zn(D₂O)₆]²⁺ about the C₃ axis. The variation of lineshape of the one-dimensional spectrum below room temperature can be explained by only the 180° flip of the water molecules. The spectrum at room temperature showed a typical shape due to the rapid 180° flip of water molecules. The change in lineshape of the one-dimensional ²H NMR spectrum is caused by the three-site jump of [Zn(D₂O)₆]²⁺ about its C₃ axis above 333 K. Information of the reorientation of [Zn(D₂O)₆]²⁺ below 333 K could not be obtained from the one-dimensional spectrum and T₁. In this temperature range, the two-dimensional exchange spectrum was effective for analysis of molecular motion. The effects of multiple motions, the 180° flip of the water molecules and the reorientation of [Zn(D₂O)₆]²⁺ about the C₃ axis, on the lineshape of the two-dimensional exchange spectrum were studied using spectral simulation.     

用核磁共振技术研究[C4mim][BF4]在重水和氘代氯仿中的聚集行为

运用核磁共振技术, 研究了室温离子液体1-丁基-3-甲基咪唑四氟硼酸盐([C4mim][BF4])在重水和氘代氯仿中的聚集行为. 实验结果表明, 随着混合体系中离子液体摩尔分数的增加, 在重水中, 离子液体阳离子上各氢原子的化学位移向低场移动, 且呈现了先急剧变化, 后趋于平缓的变化趋势; 在氘代氯仿中, 离子液体阳离子上H2的化学位移向高场移动, H4和H5以及与氮原子直接相连的甲基和亚甲基上的氢原子的化学位移都向低场移动, 且各氢原子的核磁共振信号发生了变化. 根据质量作用定律及1H NMR化学位移随浓度的变化关系计算了[C4mim][BF4]在重水中的临界聚集浓度和聚集数, 并在离子液体阴、阳离子缔合以及离子液体与溶剂相互作用的基础上对实验结果进行了讨论.     

细胞色素b5突变体P40V血红素微环境核磁共振研究

细胞色素b5是一个具有多种重要生理功能的低自旋金属蛋白, 作为呼吸链系统的主要电子传递体之一受到了广泛的重视. 为了研究细胞色素b5表面疏水斑区Pro⁴⁰在细胞色素b5结构与功能上的重要性, 本文利用定点突变技术把细胞色素b5中Pro⁴⁰突变为Val⁴⁰, 并采用1D与2D ¹H NMR的方法对其进行分析, 探讨了Pro⁴⁰突变为Val⁴⁰对细胞色素b5血红素微环境的影响.     

NMR evidence for B(C6F5)3 attack on the inward position of a highly hindered meso ansa-zirconocene

The reaction of the ansa-zirconocene meso-[C₂H₄(4,7-Me₂Indenyl)₂]ZrMe₂ with B(C₆F₅)₃ afforded, besides the expected ion pair with outward anion, also a minor isomer (molar fraction 0.043) with the bulky methylborate anion in the inward site. 2D ¹H EXSY experiments revealed exchange between the two isomers, at T > 320 K, through the migration of the anion between outward and inward sites. The presence of free B(C₆F₅)₃ fastened the exchange, suggesting B(C₆F₅)₃ attack on the zirconium bound methyl ligand of the two ion pairs.     

CuCl2和CuSO4的核磁共振系数、粘度系数及其与水分子结构的关系

测定了较低浓度范围内CuCl2、CuSO4水溶液的粘度系数(B)、核磁共振(NMR)系数(B')及其对水17O NMR化学位移的影响, 进一步计算了Cu2+、Cl-、SO2-40的粘度系数及核磁共振系数, 并与文献值进行了比较. 利用17O NMR化学位移、粘度系数和核磁共振系数与水团簇结构和水分子缔合的关系, 分析了CuCl2、CuSO4对水结构的影响. 结果表明, CuCl2和CuSO4均具有促进水分子缔合, 使水团簇加大的作用, 且CuSO4对水的缔合作用大于CuCl2, Cl-对水缔合的破坏作用大于SO2-40 . Cu2+作为顺磁离子, 在核磁共振弛豫过程中, 具有明显的缩短水中质子的自旋-晶格弛豫时间, 使谱线变宽的作用.     

Multinuclear NMR studies on substituted derivatives of Rh6(CO)16 in solution

Multinuclear NMR data (¹³C, ³¹P, ¹³C–{³¹P}, ¹³C–{¹⁰³Rh} and ³¹P–{¹⁰³Rh}) for a series of mono- and di-substituted derivatives of Rh₆(CO)₁₆ containing neutral two electron donor ligands [Rh₆(CO)₁₅L, (L=NCMe, py, cyclooctene, PPh₃, P(OPh)₃,1/2(μ₂,η¹:η¹-dppe)); Rh₆(CO)₁₄(LL), (LL=cis-CH₂=CMe-CMe=CH₂, dppm, dppe, (P(OPh)₃)₂)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the ¹³CO NMR spectra of Rh₆(CO)₁₅(PPh₃) and Rh₆(CO)₁₄(dppm) clusters have been made on the basis ¹³C–{¹⁰³Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of ³J(P–C) for terminal carbonyl ligands is discussed and the values of ³J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the ¹³C–{¹H} and ³¹P–{¹H} NMR spectra of Rh₆(CO)₁₄ (dppm) to be simulated. Variable temperature ¹³C–{¹H} NMR measurements on Rh₆(CO)₁₅(PPh₃) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh₃ on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ₃-CO's.     

四萜Methyl Sartortuoate 的分离和NMR归属

从采自海南岛三亚的扭曲肉芝软珊瑚Sarcophyton tortuosum中分离得到3个新四萜和1个已知四萜methyl sar-tortuoate (1). 利用HMQC, ¹H-¹HCOSY, HMBC等二维NMR方法首次对methyl sartortuoate (1)的所有¹H, ¹³C NMR信号进行了完全的归属.     

H/P NMR pH indicator series to eliminate the glass electrode in NMR spectroscopic pKa determinations

NMR titration is an efficient method to determine pK_a values of multiprotic acids in aqueous solution. While modern 1D/2D NMR techniques yield chemical shifts with increasing precision, the glass electrode-based pH measurement becomes the limiting factor to affect the precision of the resulting dissociation constants. The pH in the NMR tube can also be deduced from the actual chemical shift of an appropriate monoprotic indicator molecule. In the present work, the in situ NMR pH measurement has been extended for the entire pH range 0-12 using indicators with overlapping ranges of dissociation. In the first, calibrating ¹H/³¹P NMR titration, limiting chemical shifts and pK were determined for each indicator. An analysis of error propagation showed that the accuracy and precision of glass electrodes can be achieved at 1.8 < pH < 12 and even exceeded at pH extremes by NMR indicators, respectively. The assembled set of indicators was applied for in situ pH monitoring in the following “electrodeless” ¹H/³¹P NMR titration of a newly synthesized aminophosphinophosphonic acid. Multivariate nonlinear parameter estimation was used to calculate the pK values that were confirmed by potentiometric titrations.     

NMR spectra of salicylohydroxamic acid in DMSO-d6 solution: a DFT study

The ¹H, ¹³C and ¹H, ¹³C COSY NMR spectra of salicylohydroxamic acid (sha) were measured in DMSO-d₆ solution. The B3LYP GIAO method with the 6-311++G(d,p) basis set was chosen to reproduce the experimental spectra. All possible zusammen and entgegen conformers of monomeric sha were computed. After geometry optimisation (B3LYP/6-311++G(d,p)) only nine independent models of the molecule were shown to be stable. Additionally, the NMR chemical shifts of the Onsager model of the most stable monomer were calculated. The computed chemical shifts for the labile protons for all aforementioned geometries meaningfully underestimated experimental results suggesting the existence of the H-bonded structure of sha in DMSO solution. The most probable two dimeric structures along with two solvent-bounded aggregates were subsequently calculated at the same level of theory. The best agreement was obtained for sha H-bonded with two DMSO molecules (confirmed by the absence of concentration effect). The relative error not exceeding 10 and 4% for chemical shifts in ¹H and ¹³C NMR spectra of sha–(DMSO)₂, respectively, showed that the applied method with the B3LYP/6-311++G(d,p) basis set was efficient to predict the NMR shifts of a compound with strong H-bonds. Thus, this allows to assign properly NMR resonances to specific structure formed in DMSO solution.     

Dilatometric, dielectric and NMR studies of structural phase transitions of the (CH3NH3)3Bi2Cl9 (MACB) crystals

The phase transitions and molecular motions of the methylammonium cations were investigated in the (CH₃NH₃)₃Bi₂Cl₉ (MACB) crystal by dilatometric and dielectric measurements, and by the measurements of the ¹H spin-lattice relaxation times and second moment of the ¹H NMR absorptions over a wide temperature range. Structural phase transitions, weakly first order at 247 K (III ↔ II) and continuous at 352 K (II ↔ I), were detected by the dilatometric technique. The ¹H NMR measurements revealed the presence of the uniaxial reorientations of the three non-equivalent methylammonium cations in the lowest temperature phase (III).     

Deuteron NMR spin–lattice relaxation of NH3D ions in partially deuterated (NH4)2SnCl6 and NH4ClO4

Deuteron spin–lattice relaxation is studied in 5% and 100% deuterated ammonium hexachlorostannate and perchlorate. The relaxation rate is observed to be independent of deuteration down to temperatures slightly lower than that of the maximum. At lower temperatures the rate of the 5% deuterated sample exceeds that of the 100% deuterated sample by four and two orders of magnitude in ammonium hexachlorostannate and perchlorate, respectively. The angular dependence of the deuteron relaxation rate in 5% deuterated ammonium hexachlorostannate at 6 K is explained in terms of existing models on quadrupolar relaxation. In 5% ammonium perchlorate one hydrogen equilibrium position, which lies on the preferred axis for 120° rotations, has a larger probability to be occupied by the deuteron of NH₃D⁺ ions. The deuterons at the other positions are still performing rotational jumps about the preferred C₃ axis and also about the other threefold axes, although at a slower rate. Such observations require a reconsideration of the relaxation process. A somewhat more general expression is derived for the relaxation rate, which agrees with the experimentally observed angular dependence for 5% deuterated ammonium perchlorate at 60 K. At lower temperatures the quadrupole coupling of the deuterons at the preferred axis may become practically time-independent. Then a significant contribution to the relaxation rate can be provided by the deuteron–proton magnetic dipolar interaction, which is still fluctuating fast via the rotation of the three protons about the axis through the stationary deuteron.     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).