Electron paramagnetic resonance in various gadolinium complexes

Journal of Structural Chemistry -     

NMR methods for molecular structure studies of paramagnetic lanthanide complexes in solutions. Applications to crown ether complexes

The literature data on NMR spectroscopic methods for investigation of the spatial structure and molecular dynamics of lanthanide complexes with macrocyclic potyethers in solutions are reviewed. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 714–730, July–August, 1998.     

Lanthanide-ion-induced paramagnetic shifts in NMR spectra in aqueous solutions

Theoretical and Experimental Chemistry -     

Theory of NMR shifts and endor spectroscopy in paramagnetic complexes

A theory of NMR and ENDOR spectroscopy in paramagnetic complexes is presented. The relevant matrix elements of both the contact and pseudo-contact interaction within the eigenstates of the magnetic electrons are treated exactly. It is shown, that the interactions depend upon the azimuthal angle ? of the resonant nucleus, even for high point symmetries of the paramagnetic center. In the case of NMR shift measurements, where the spin-lattice relaxation time is short, the interaction of the nuclear spin with the electron's spin and orbital motion can be described by a temperature-dependent induced magnetic field which is not parallel to the applied field. The results differ even in lowest order of the multipole expansion from previous theories. The pseudo-contact shift for rare-earth complexes is correlated to susceptibility in a modified form. In iron-series complexes, such a correlation is generally not possible. Here, the familiar point-dipole approximation used in earlier theories is valid only, if the orbital angular momentum is quenched or if the resonant nucleus lies on the p-fold rotation axis and p ≥ 2.     

Arylgold(I) complexes from base-assisted transmetalation: structures, NMR properties, and density-functional theory calculations

The synthesis of gold(I) complexes of the type LAuR (L = PCy(3), IPr; R = aryl; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) starting from LAuX (X = Br, OAc) and boronic acids in the presence of Cs(2)CO(3) has been investigated. The reactions proceed smoothly in good to excellent yields over the course of 24-48 h in isopropyl alcohol at 50-55 °C. The aryl groups include a variety of functionalities and steric bulk, and in two cases, are heterocyclic. All of the products have been characterized by multinuclear NMR spectroscopy and elemental analysis and most by X-ray crystallography. This work affirms that, almost without exception, base-assisted auration is a useful and reliable way to form gold-carbon bonds.     

Paramagnetic NMR spectroscopy and density functional calculations in the analysis of the geometric and electronic structures of iron-sulfur proteins

Paramagnetic NMR spectroscopy has been underutilized in the study of metalloproteins. One difficulty of the technique is that paramagnetic relaxation broadens signals from nuclei near paramagnetic centers. In systems with low electronic relaxation rates, this makes such signals difficult to observe or impossible to assign by traditional methods. We show how the challenges of detecting and assigning signals from nuclei near the metal center can be overcome through the combination of uniform and selective 2H, 13C, and 15N isotopic labeling with NMR experiments that utilize direct one-dimensional (2H, 13C, and 15N) and two-dimensional (13C-X) detection. We have developed methods for calculating NMR chemical shifts and relaxation rates by density functional theory (DFT) approaches. We use the correspondence between experimental NMR parameters and those calculated from structural models of iron-sulfur clusters derived from X-ray crystallography to validate the computational approach and to investigate how structural differences are manifested in these values. We have applied this strategy to three iron-sulfur proteins: Clostridium pasteurianum rubredoxin, Anabaena [2Fe-2S] ferredoxin, and human [2Fe-2S] ferredoxin. Provided that an accurate structural model of the iron-sulfur cluster and surrounding residues is available from diffraction data, our results show that DFT calculations can return NMR observables with excellent accuracy. This suggests that it might be possible to use calculations to refine structures or to generate structural models of active sites when crystal structures are unavailable. The approach has yielded insights into the electronic structures of these iron-sulfur proteins. In rubredoxin, the results show that substantial unpaired electron spin is delocalized across NH...S hydrogen bonds and that the reduction potential can be changed by 77 mV simply by altering the strength of one of these hydrogen bonds. In reduced [2Fe-2S] ferredoxins, hyperfine shift data have provided quantitative information on the degree of valence trapping. The approach described here for iron-sulfur proteins offers new avenues for detailed studies of these and other metalloprotein systems.     

A justification for using NMR model-free methods when investigating the solution structures of rhombic paramagnetic lanthanide complexes

The detailed analysis of the 1H NMR hyperfine shifts according to the model-free methods shows that the semi-rigid monometallic complexes [Ln(L)(NO3)3] (Ln = Eu-Yb) are isostructural in solution. The associated separation of contact and pseudo-contact contributions to the hyperfine NMR shifts in each rhombic lanthanide complex at room temperature provides paramagnetic susceptibility tensors whose principal magnetic axes match the expected symmetry requirements. Moreover, both axial (Delta chi(ax)) and rhombic (Delta chi(rh)) paramagnetic anisotropies display satisfactory linear dependence on Bleaney's factors, a correlation predicted by the approximate high-temperature expansion of the magnetic susceptibility limited to T(-2). Consequently, the simple, and chemically attracting NMR model-free methods are not limited to axial systems, and can be safely used for the investigation of the solution structures of any lanthanide complexes. Molecular-based structural criteria for the reliable estimation of paramagnetic susceptibility tensors by NMR are discussed, together with the assignment of the labels of the crystal-field and magnetic axes within Bleaney's approach.     

Simultaneous adiabatic spin-locking cross polarization in solid-state NMR of paramagnetic complexes

Continuous-wave irradiations cross polarization and its variations had not been a popular choice for sensitivity enhancement in paramagnetic solids due to the large spectral broadening and the effect of fast relaxation on both the source and target spins. Furthermore, with the application of very-fast sample spinning, which is the prerequisite for high-resolution purposes, polarization transfer over a large bandwidth is further degraded. In this work, we report a wideband sensitivity enhancement in paramagnetic solid with our recently developed technique, simultaneous adiabatic spin-locking cross polarization, SADIS CP. Experiments were demonstrated with Cu(II)(d,l-alanine)₂ · H₂O under high-static field of 14.1 T and very-fast sample spinning of 31 kHz.     

Local diffusion in paramagnetic solutions by NMR relaxometry at one frequency

The relative diffusion coefficient D of a paramagnetic species and a diamagnetic probe molecule bearing nuclear spins is obtained from their measured relaxation times T1 and T2 (or T1rho). This is achieved by introducing the longitudinal relaxivity, r1, a linear expression of 1/T1, and the mixed relaxivity, rmix, a linear expression of 1/T1 and 1/T2 (or 1/T1rho). Under weak assumptions, D is proportional to (rmix - r1) to the power -2/3 and to rmix to the power -1, with easy-to-determine proportionality factors. The method is noninvasive and easy to use on standard NMR spectrometers and imagers. It is validated through the study of various solutions of a Gd(III)-based contrast agent for magnetic resonance imaging.     

Conformational Analysis of Open-Chain 1,2:3,4-Diepoxides: Comparison of crystal structures,NMR data,and molecular-orbital calculations

Several pairs of diastereoisomeric open-chain 1,2:3,4-diepoxides with different substitution patterns were prepared (see 3–9 ). As far as possible, crystal structures were determined to corroborate the relative configurations and to give insight into the solid-state conformations of these compounds. The comparison with our earlier molecular-orbital calculations and with ¹H-NMR measurements shows that the solid-state conformations of eight out of the nine open-chain 1,2:3,4-diepoxides, whose crystal structures had been determined, correspond to minima on the calculated energy profiles for these compounds or for closely related derivatives. In solution, highly substituted diepoxides of the erythro-series (e- 6 , e- 7 , e- 9 ) seem to prefer the same conformation as in the crystal. The solution conformations of all other diepoxides differ from the arrangement in the solid state.     

NMR spectra of paramagnetic complexes of 1-vinylimidazole with iron group metals

The high-resolution ¹H and ¹³C NMR spectra of 1-vinylimidazole complexes with iron group metals were recorded. The contact coupling in these systems was established in the ¹H and ¹³C NMR spectra. The applicability of the NMR spectra transformed by long-range hyperfine coupling for elucidating the molecular structure of the ligand was shown. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1430–1433, June, 2005.     

Cyanide (13)C NMR hyperfine shifts in paramagnetic cyanide-bridged mixed-valence complexes

Paramagnetic (hyperfine) NMR shifts in the (13)C cyanide bridge and (31)P resonances in a set of mixed valence complexes [(eta(5)-C(5)R(5))Ru(PPh(3))L((13)CN)Ru(NH(3))(5)](n+) (R = H; L = PPh(3), CO, NO(+); R = Me; L = PPh(3)) are sensitive to the extent of intermetallic charge-transfer, and are strongly solvent dependent.