Solvation of Na+ in N,N-dimethylformamide + methanol solutions. A nuclear magnetic relaxation study using dynamic solvent isotope effects

Inter- and intramolecular nuclear magnetic quadrupole relaxation measurements have been used to study the system methanol (CH₃OH)+ N,N-dimethylformamide (DMF)+NaI at 25°C. The dynamic behavior of the solvent molecules was investigated, throughout the composition range of the binary mixtures, by means of ¹⁴ N relaxation of DMF and ² H of methanol-d ₁ (CH ₃ OD). The intermolecular relaxation of ²³ Na⁺ in pure DMF was used to obtain information about the symmetry of the solvent electric dipole arrangement in the solvation sphere of the ion. The investigation of preferential solvation around Na⁺ in the binary mixtures was carried out by means of ²³ Na⁺ relaxation measurements using, for the first time, both the CH ₃ OH/CD ₃ OD and the DMF/DMF-d ₇ dynamic isotope effect. The results show that, throughout the composition range, there is preferential solvation by DMF. Furthermore, the use of the isotope effects of both components allowed for the first time a basic check of the reliability of the method since we obtained two independent sets of data for the composition of the Na⁺ solvation shell in the mixtures. The consistency of the two separate data sets demonstrates that the application of the dynamic isotope effect represents a powerful tool in preferential solvation studies.     

NMR spin–lattice relaxation time measurements in organochalcogen compounds

¹H and ⁷⁷Se spin-lattice relaxation times have been measured for the series of organochalcogen compounds MeE(CH₂)nEMe (E=S, Se, n=0–3; E = O, n = 1, 2). The methyl and methylene proton T₁ values decreased with increasing mass/size of the chalcogen and with increasing methylene chain length. The values are primarily due to intra- and inter-molecular dipole-dipole relaxation with proton-proton cross-relaxation effects playing a significant role. ⁷⁷Se T₁ values are dominated by spin rotation and chemical shielding anisotropy mechanisms, their relative importance depending on the size of the molecule and temperature of measurement.     

Nuclear spin relaxation dynamics of 13CO2 sorbed in polyisobutene rubber

Recently we presented the dynamics of ¹³CO₂ molecules sorbed in silicone rubber (PDMS) ascertained from spin relaxation experiments. Results of a similar investigation for ¹³CO₂ sorbed in polyisobutene (PIB) are presented in this report. The spin-lattice and spin-spin relaxation times as well as nuclear Overhauser enhancements (NOE) were determined as a function of temperature and Larmor frequency. The relaxation mechanisms found to be important for ¹³CO₂/PIB system are intermolecular dipole-dipole relaxation and chemical shift anisotropy with a minor contribution from spin rotation relaxation. We have determined the parameters which characterize correlation times for ¹³CO₂ collisional motion, rotational motion, and translational motions in the PIB. The self-diffusion coefficient of 5.15 × 10^?8 cm²/s obtained from the nuclear magnetic resonance (NMR) data is close to the literature value of the mutual diffusion coefficient of CO₂ in PIB at 300 K obtained from permeability measurements. In contrast to the case of CO₂/PDMS in which a broad distribution (characterized by a fractional exponential correlation function of the Williams-Watts type with α = 0.58) is observed, a sharp distribution with a fractional exponent, α, of 0.99 is found for the CO₂/PIB system. Instead of assuming an Arrhenius type temperature dependence, we used a Williams-Landel-Ferry type temperature dependence and found it to be better suited to describe the behavior of this system. PIB is a densely packed “strong” chain polymer which responds gradually to the temperature variation and gas sorption. In contrast PDMS is a relatively loosely packed “fragile” polymer with a propensity to exhibit rapid dynamic responses to the temperature change and gas sorption. © 1993 John Wiley & Sons, Inc.     

Collision-induced and infrared multiphoton dissociation studies on M(acetone)2 + (M=Al,Fe, Co,Cu, ScO) in the gas phase

In this paper we report an extension of our earlier study on the structure of Alfacetone)₂ ⁺ Collision-induced dissociation (CID) on MfacetoneXacetone-d₆)⁺ for M = Al, Fe, Co, and Cu yields primarily, if not exclusively, nearly equal amounts of acetone and acetone-d₆. Likewise, infrared multiphoton dissociation (IRMPD) at 10.6 μm yields, exclusively, nearly equal losses of the labeled and unlabeled acetones. These results suggest that the two acetone ligands bind in an equivalent fashion. Sc⁺ was also studied, which proved to be the most interesting. Sc⁺ reacts with acetone to form primarily ScO⁺, which undergoes higher order reactions leading to several products including ScO(acetone)₂ ⁺. IRMPD on this ion produces ScO(acetone-d₆)(CD₂CO)⁺, while its perdeuterated analog also produces ScO(acetone-d₆)⁺ in addition to ScO(acetone-d₆(CD₂CO)⁺. The IRMPD results are supplemented by studying the primary and higher order reactions of Sc⁺ with acetone, as well as the CID of ScO(acetone)₂ ⁺. Finally, a qualitative assessment of the infrared photodissociation cross sections is given. It is found that the relative photodissociation cross sections follow the orders Co(acetone-d₆)₂ ⁺ > Co(acetone)(acetone-d₆) > Co(acetone)₂ ⁺ and Co(acetone-d₆)⁺ > Co(acetone)⁺.     

Nuclear magnetic relaxation and ionic solvation of23Na+ and81Br− in aqueous mixtures of simple amides

Ion-solvent interactions of Na⁺ and Br^– in binary aqueous mixtures of formamide,N-methylformamide (NMF), andN,N-dimethylformamide (DMF) are studied by use of²³Na and⁸¹Br magnetic relaxation times, extrapolated to zero salt concentration. The relaxation times, which are controlled by quadrupolar interaction, have been measured over the complete mixture range and are compared with a simplified theoretical formula. It turned out that the²³Na⁺ relaxation in H₂O-formamide and H₂O-NMF mixtures is in excellent agreement with theoretical predictions, implying nonpreferential solvation of Na⁺ in these systems. Small deviations of experimental from theoretical results in H₂O+DMF possibly indicate weak selective hydration of the cation. In the case of the anionic nuclei⁸¹Br^–, deviations from the theoretical curve occur which are to be expected, especially for systems where hydrophobic effects play a role. On the other hand, it is demonstrated that these deviations can easily be explained within the electrostatic theory by differences in structural details of the anionic solvation sphere in the mixtures compared to the pure solvents.     

<Emphasis Type="Italic">N,N</Emphasis>′-bis(<Emphasis Type="Italic">ortho</Emphasis>-acylaryl)diaza-18-crown-6 ethers: Synthesis,complexation in solution,and crystal structure of the complex with lead perchlorate

Two new lariat ethers were obtained from N,N′-diaryldiaza-18-crown-6 (Ar = 2-formyl-4-methylphenyl (II) and 2-benzoyl-4-methylphenyl (III)). In the ethers obtained, the carbonyl O atoms act as additional electron-donating sites. Complexation of lariat ethers II and III with metal cations in solution was studied by ¹H NMR spectroscopy (acetone-d₆, methanol-d₄). The stability constants of the resulting complexes were determined. For lariat ether III and its complexes, the magnetic anisotropy of the benzoyl groups substantially influences the chemical shifts of the protons of the macrocycle. The stability of the complexes increases from ether II to III and in the order K⁺ < Ba²⁺ < Pb²⁺. Complexes with La³⁺ were not obtained. The complex of lariat ether II(L) with Pb(ClO₄)₂, [PbL(H₂O)](ClO₄)₂ · H₂O, was characterized by X-ray diffraction. The Pb²⁺ cation is in the cavity of the lariat ether and is coordinated by the formyl O atoms on one side of the macrocycle plane and by the water molecule on the other side (C.N. 9).     

119Sn spin–lattice relaxation times and nuclear Overhauser enhancement factors in some organotin compounds

Dipole-dipole relaxation via non-bonded protons is an important relaxation mechanism for¹¹⁹Sn in tri-n-propyltin and tri-n -butyltin compounds. This causes a negative nuclear Overhauser effect, arising from the negative magnetogyric ratio, which in some cases nulls the signal. The relative contributions from the spin-rotation and dipole-dipole mechanisms vary: larger molecules have lower spin-rotation and higher dipolar relaxation rates. The practical significance of large nuclear Overhauser enhancement factors in recording ¹¹⁹Sn spectra and the relation of the dipole-dipole contribution to the molecular motion and of the spin-rotation contribution to the absolute shift scale for ¹¹⁹Sn are discussed.     

Fast 1H NMR relaxation in some ruthenium hydrides

We report here the synthesis of the new hydride complexes (C₅H₄CH(CH₂CH₂)₂NMe)- RuH(PPh₃)₂ (1) and [(C₅H₄CH(CH₂CH₂)₂NHMe)-RuH(PPh₃)₂](BF₄) (2), the X-ray crystal structures of 1 and 2, and an unprecedented observation of extremely short relaxation times in a monohydride complex as well as in the reaction of CpRuH(PPh₃)₂ with a variety of acidic proton donors. The relaxation is much faster than expected for a dipole-dipole process involving the two dihydrogen-bonded protons, but no origin for the effect could be suggested.     

<Superscript>1</Superscript>H and <Superscript>31</Superscript>P nuclear spin-lattice relaxation in C-phosphorylated oximes

The ¹H spin-lattice relaxation times of the proton-bearing groups and the ³¹P spin-lattice relaxation times in C-phosphorylated oximes R¹C(=NOH)P(=O)R²R³ (R¹ = Ph, R² = R³ = OMe; R¹ = Ph, R² = OMe, R³ = OCH²CH²Br; R¹ = PhCH², R² = R³ = OCHMe²) and dioxime R²P(=O)C(=NOH)(CH₂)₄C(=NOH)P(=O)R² (R = OMe) in DMSO-d₆ were measured. The characteristic reorientation times of the whole molecules were estimated using the measured values of the ¹H relaxation times and the results of semiempirical PM3 quantum chemical calculations of the molecular geometries. The reorientation times were used to identify the contributions of different relaxation mechanisms to the rate of ³¹P spin-lattice relaxation. The anisotropy of the chemical shielding of ³¹P nuclei was evaluated from the difference between the ³¹P relaxation rates measured at 101.27 and 161.92 MHz.     

Natural abundance nitrogen-15 n.m.r. spectroscopy. Spin–lattice relaxation in organic compounds

The small negative magnetogyric ratio (γ) of the ¹⁵N nucleus decreases the efficiency of ¹⁵N? ¹H dipole-dipole relaxation to about 25% of that for an analogous ¹³C nucleus. This may lead to greater competition from other relaxation mechanisms in ¹⁵N n.m.r. and consequent partial or total quenching of the negative nuclear Overhauser effect (NOE). In unfavorable circumstances nulling of the ¹⁵N resonance can occur. Previous ¹⁵N relaxation studies have examined isotopically enriched, low molecular weight compounds. The present study examines several small to intermediate size organic compounds containing nitrogen at natural isotopic abundance. In contrast to some of the earlier studies, ¹⁵N? ¹H dipolar relaxation was found to be dominant for protonated nitrogen atoms, even for two tertiary nitrogens (the tertiary amine nitrogen in 1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a] quinolizine and the oxime nitrogen in 3-methyl-2-pentanone ketoxime). The magnitude of the NOE and the moderate value of T₁ indicate effective dipolar relaxation from neighboring but not directly bonded protons in these cases. Nitro groups were found, as expected, to have predominant contributions from non-dipolar mechanisms, and in one case (2-methyl-2-nitro-1, 3-propanediol) signal nulling (NOE of η = ?1) was observed. The effect of paramagnetic impurities was demonstrated for ethanolamine, which contains a basic nitrogen. In this case T₁^DD(¹⁵N? ¹H) = 4·3 s; added Ni(acac)₂ at 1 × 10^?4 Molar reduced the ¹⁵N T₁ to 0·065 s and consequently the NOE to η = 0.     

Rotational molecular motion and solvation of Na+ and Cs+ in water-dimethylacetamide. A nuclear magnetic relaxation study

Nuclear magnetic relaxation by intra- and intermolecular quadrupoleelectric field gradient interaction has been used for the study of the systems DMA-water-NaI and DMA-water-CsI at 25°C.¹⁴N relaxation of DMA and²H relaxation of D₂O measured over the complete mixture range reveal the behavior of the rotational molecular motion of the two solvent components. For both solvent components a marked maximum of the reorientational correlation time has been found, reflecting hydrophobic effects and strong DMA-water interaction. The quadrupolar relaxation rates of²³Na⁺ and¹³³Cs⁺ in pure DMA were evaluated giving an indication that the electric solvent dipoles in the solvation shell are not located on positions of cubic symmetry. A quantitative study of preferential solvation of the cations in the mixed solvent has been performed by using the H₂O-D₂O isotope effect on²³Na⁺ and¹³³Cs⁺ relaxation. For both cations an obviously typical change in the selectivity occurs. In the range l>x _{H2 O}>0.7 we find weak preferential hydration, but in the range 0.7>xH ₂ O>0 strong preferential solvation by DMA is reflected.     

The carbon-13 chemical shifts and the analysis of the relaxation times T1 and long range 13C−1H coupling constants of quinoline and of 1-(X-quinolyl)ethyl acetate derivatives

The ¹³C chemical shifts and the ¹³C−¹H coupling constants of quinoline (1-(X-quinolyl)ethyl acetate derivatives (where X=−CH(OAc)CH₃ substituted at positions 2,4,5–8) are reported. Substituent chemical shift (SCS) effects for the ethyl acetate group are additive at all positions. A substantial upfield shift of 4.5 and 4.8 ppm was observed at C-4 and C-5, arising from the peri interaction of 5- and 4-ethyl acetate substituents respectively. A vicinal (peri) ³J CCCH coupling constant of approximately 5 Hz is observed between both C₅−H₄ and C₄−H₅. Carbon-13 relaxation times (T₁) and nuclear Overhauser enhancements (η) have been measured for quinoline and its derivatives, and the contributions of dipolar, T₁^DD, and spin rotation, T₁^SR, relaxation have been determined. Intramolecular dipole-dipole interactions are found to provide by far the most important spin-lattice relaxation mechanism whenever protons are bound directly to the carbons under investigation. Non-protonated ring carbons are relaxed by both DD and SR mechanisms. Anisotropic motion has an easily observable effect on the DD contribution to T₁, and can form the basis for spectral assignments, as in 1-phenylethyl acetate. Long-range ¹³C−¹H coupling constants were observed both between ring carbons and between ring carbons with ring side-chain hydrogens. These results have been used for the structure determination of the title compounds.     

Vibrational relaxation in the group IVA trimethylmetal chlorides

The temperature dependence of the polarized and depolarized Raman spectra of the ν₂, ν₄, ν₆ and ν₇ modes were measured for t-butyl chloride and the analogous group IVA trimethylmetal chrlorides (silicon, germanium and tin). Analysis of the lineshapes revealed that isotropic second moments and vibrational relaxation times for a given mode remained approximately constant through the series. This tranferability of relaxation parameters between molecules extended to modulation times calculated from the Kubo formalism. The above results are in contrast to earlier studies on molecules of dissimilar structure. They provide some preliminary evidence that the mechanism of vibrational relaxation may be the same for equivalent modes in members of the series.     

Comparison between Roesy and 13C NMR Complexation Shifts in Deriving the Geometry of Inclusion Compounds: A Study on the Interaction between Hyodeoxycholic Acid and 2-Hydroxypropyl-β-Cyclodextrin

Abstract

The formation and geometry of the hyodeoxycholic acid (HDCA)/2-hydroxypropyl-β-cyclodextrin (HPβCD) complex in methanol-d₄ solution was determined through a rotating frame nuclear Overhauser (ROESY) experiment. The reported results confirmed those independently and previously obtained though the use of ¹³C complexation shifts in the same solvent. The ¹³C approach, which needs shorter experimental times and is currently used in the study of HPβCD/bile acid systems, was then substantiated.     

Molecular relaxation processes in very dilute systems: A 13C NMR study of alcohols in alkanes

¹³C T₁ relaxation times have been determined for n-butanol in C₆D₁₂ in the concentration range 0.001 ? _x ? 1 (using ¹³C labelled alcohol) and for t-butanol in the range 0.01 ? _x ? 1. In the former case, this has allowed us to probe molecular mobility down to the region of monomeric alcohols. Comparison with previous results from measurements of ¹H chemical shifts, dielectric relaxation, and the picosecond dynamics of electron solvation allows us to build up a detailed picture of molecular clustering and liquid structure in alkane—alcohol mixtures. For n-butanol, the local liquid structure is established by x = 0.2 while t-butanol does not appear to form aggregates larger than trimers until x = 0.5.     

A hydrogen-1, chlorine-35, and lanthanum-139 NMR coordination study of the lanthanum (III) ion in aqueous solvent mixtures

A La(III) hydration study has been carried out for solutions of La(ClO₄)₃ and, in a preliminary way, La(NO₃)₃ in aqueous mixtures with acetone-d₆ and Freon-12, using hydrogen-1, chlorine-35, and lanthanum-139 NMR spectroscopy. Low temperature, proton magnetic resonance experiments allowed the direct observation and area evaluation of separate signals for water molecules in the primary solvation shell of La(III) and in bulk medium. Measurements over a wide range of salt and solvent concentration gave a maximum La(III) hydration number of 6 and no evidence for inner-shell ion-pairing in La(ClO₄)₃ solutions. Chlorine-35 chemical shift and linewidth data in these solutions confirmed the absence of contact ionpairing. Hydration numbers of 3–4 for La(III) in several La(NO₃)₃ solutions clearly indicated inner-shell complex formation. Lanthanum-139 chemical shift and linewidth measurements for these systems revealed the presence of some process, possibly hydrolysis, in the La(ClO₄)₃ solutions at extremely high acetone-d₆ concentrations.     

Single vibronic level fluorescence and relaxation spectra of s-tetrazine-d0 and d2 vapors

The third strongest cold band in the 5500Å absorption spectrum of s-tetrazine vapor is assigned to 6b₀² by analysis of single-vibronic-level (SVL) fluorescence spectra obtained with a tunable cw dye laser. Fermi resonance model calculations for the doublet 6a₀¹…6b₀² simulate the perturbations of relative intensities in ν_6a^″ fluorescence progressions which arise fron interference between the two terms of the Franck-Condon factors. Addition of a quartic anharmonic term to the quadratic ν_6b^′ potential accounts for the observed spacing of the observed 6b¹ and 6b² levels and suggests a likely candidate for the heretofore missing 6b₀⁴ member of the Fermi resonance triad. Weak bands with in-plane polarization are revealed in fluorescence and contribute to a list of newly measured frequencies of the ground state. Experiments with added n-pentane show that rotational relaxation proceeds at the hard-sphere rate while vibrational relaxation is about five times slower. Vibrational relaxation exhibits non-statistical distribution in the early stages; it is rather distinctive when starting from the zero-level of the excited state, but is reminiscent of earlier work (on benzene) when starting from the 16b¹ level. Identification of the level 6b¹ is supported by these relaxation experiments.     

31P-NMR. Measurements on Palladium-Phosphine Complexes. Nuclear overhauser effects and spin-lattice relaxation times

The ³¹P{¹H} nuclear Overhauser effects (NOE's) and ³¹P-spin-lattice relaxation times (T₁) for a series of trans-[PdCl₂P₂], P ? PEt₃, PPr₃ⁿ, PBu₃ⁿ, PMe₂Ph, PMePh₂, P(p-Tol)₃, P(cyclohexyl)₃ complexes are reported. Both the NOE and T₁ values depend upon the choice of solvent. The dipole-dipole mechanism dominates the spin-lattice relaxation of the coordinated phosphorus atom with the T₁ values for the PEt₃, PPr₃ⁿ, and P (cyclohexyl)₃ complexes decreasing with increasing molecular weight of the phosphine.     

Relative concentrations and relaxation properties of isomeric alkyl radicals in γ-irradiated n-alkane single crystals

The relative concentrations of alkyl radicals CH₃C?HCH₂R(I) and R'CH₂C?HCH₂R''(II) were measured at low microwave power in some n-alkane single crystals γ-irradiated at 77 K to a dose of 1 Mrad. The relative concentration of radical (II) increased as the number of carbon atoms became larger. The amount of radical (I) was in agreement with a mechanism where all CH bonds in an n-alkane molecule are raptured with the same probability followed by an isomerization of primary alkyl radicals to radical (I). In n-decane for instance this mechanism predicts 45.5% of radical (I) compared to the experimental value of 45.5%. Saturation measurements of radical (I) and radical (II) under slow passage condition showed that the spin-lattice relaxation time T₁ is shorter for radical (I) (ca. 3 × 10^?4s) than for radical (II) (ca. 80 × 10^?4s), while the spin-spin relaxation times T₂ are similar (ca. 2 × 10^?8s). The relatively short relaxation time T₁ in radical (I) is thought to originate from higher mobility of the end of the alkane chain, where the unpaired electron is localized, and also a modulation of the hyperfine coupling from protons in the nearby rotating methyl group. The broad linewidth in irradiated protiated cyrstals was by comparison with results from deuterated matrices concluded to depend on slightly distorted radicals in damaged regions (spurs, short tracks, blobs) and not on electron dipole-dipole interactions. Unresolved γ-proton couplings in radical (I) are thought to cause the spin-flip transitions at high microwave power.