The gas-phase loading of [Zn4O(bdc)3] (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound [Ru(cod)(cot)] (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state (13)C magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 degrees C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state (2)H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the [Ru(cod)(cot)]3.5@MOF-5 inclusion compound at the milder condition of 25 degrees C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by (13)C MAS NMR, PXRD, and TEM.

In this paper a quantitative explanation for a diamagnetic ortho/para H2 conversion is given. The description is based on the quantum-mechanical density matrix formalism originally developed by Alexander and Binsch for studies of exchange processes in NMR spectra. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a three spin system, the reactions of the hydrogen gas with the catalysts are treated as a phenomenological rate process, described by a rate constant. Numerical calculations reveal that for nearly all possible geometrical arrangements of the three spin system an efficient spin conversion is obtained. Only in the chemically improbable case of a linear group H-X-H no spin conversion is obtained. The efficiency of the spin conversion depends strongly on the lifetime of the H-X-H complex and on the presence of exchange interactions between the two hydrogens. Even moderate exchange couplings cause a quench of the spin conversion. Thus a sufficiently strong binding of the dihydrogen to the S spin is necessary to render the quenching by the exchange interaction ineffective.

In this paper a possible explanation for an unexpected ortho/para-water ratio in the gas clouds of comets is given. The description is based on the quantum-mechanical density matrix formalism and the spin temperature concept. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a four spin system, created by two nearest neighbour water molecules, spin eigenstates and their dynamics under the influence of their mutual dipolar interactions are studied. It is shown that a fast conversion between ortho- and para-states occurs on a msec time scale, caused by the intermolecular homonuclear magnetic dipolar interaction. Moreover the spin eigenstates of water in an ice crystal are determined by magnetic dipolar interactions and are not given by normal ortho- and para-H2O states of gaseous water. As a result of this the spin temperature of gaseous water evaporated from ice depends strongly on its evaporation history and the ortho/para-ratio of water molecules are only an indirect measure of the temperature of ice crystals from where they descend. This result could explain the unexpected experimentally observed ortho/para-ratios in the clouds of comets.

The phenomenon of exchange coupling is taken into account in the description of the magnetic nuclear spin conversion between bound ortho- and para-dihydrogen. This conversion occurs without bond breaking, in contrast to the chemical spin conversion. It is shown that the exchange coupling needs to be reduced so that the corresponding exchange barrier can increase and the given magnetic interaction can effectively induce a spin conversion. The implications for related molecules such as water are discussed. For ice, a dipolar magnetic conversion and for liquid water a chemical conversion are predicted to occur within the millisecond timescale. It follows that a separation of water into its spin isomers, as proposed by Tikhonov and Volkov (Science 2002, 296, 2363), is not feasible. Nuclear spin temperatures of water vapor in comets, which are smaller than the gas-phase equilibrium temperatures, are proposed to be diagnostic for the temperature of the ice or the dust surface from which the water was released.

The (2)H quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state (2)H MAS NMR techniques are used in the investigations of two ruthenium clusters, D(4)Ru(4)(CO)(12) (1) and D(2)Ru(6)(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the (2)H MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu(6)(CO)(18)](-) (2(-)) and cationic [D(3)Ru(6)(CO)(18)](+) (2(+)). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the (2)H nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles.

The (2)H solid-state NMR spectra of the transition metal complexes Tp*RuD(THT)(2) (1a), Tp*RuD(D(2))(THT) (1b), Tp*RuD(D(2))(2) (1c), Cp*RuD(3)(PPh(3)) (2) and RuD(2)(eta(2)-D(2))(2)(PCy(3))(2) (3) have been measured in a wide temperature range. These compounds were chosen as potential model systems for hydrogen surface species in Ru-nanoparticles. The deuterium quadrupolar coupling constants Q(cc) and asymmetry parameters were extracted by (2)H NMR line-shape analysis. The Q(cc) values of the deuterons bound to the metal vary between 13 kHz and 76 kHz. In addition all spectra show that some of the deuterium is incorporated into carbon positions exhibiting quadrupolar coupling constants in the range of 134 kHz to 192 kHz. The room temperature spectra contain an additional weak very narrow line which was assigned to deuterons exhibiting a high mobility. These deuterons are attributed to crystallographic impurity and partially to D(2) molecules which lost by the complexes. The temperature where their motion is quenched and the types of these motions depend on the chemical structure. We propose to use the values of the quadrupolar coupling constants measured in order to characterize different hydrogen species on the surface of Ru-nanoparticles.

Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. 2H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of 2H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (deltanuQ) and the asymmetry parameter (etaQ). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. 2H NMR properties of five mononuclear ruthenium complexes (namely Cp*RuD3(PPh3), Tp*RuD(THT)2, Tp*RuD(D2)(THT) and Tp*RuD(D2)2 and RuD2(D2)2(PCy3)2) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta2-H2), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although 2H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR.

In the current study two new classes of stabile, catalytic active nanomaterials are investigated. The first class of nanoparticles consists of an inner metal core. To stabilize their structure the metal core is surrounded by organic ligands or embedded in a polymer. The second class consists of catalysts immobilized on mesoporous silica supports of SBA-3 type silica. Employing a combination of 1 H, 2 H, 13 C and 29 Si-solid state NMR spectroscopy the structure of the catalysts is analyzed. As a simple model for the catalytic properties of the particles, the activation of 2 H 2 gas on the surface of the particles is studied. Employing 1 H and 2 H gas phase NMR the kinetics of simple catalytic model reactions is studied. Employing 2 H-NMR solid state NMR spectroscopy, the interaction of the metal surface with the substrate is characterized and kinetic data, which characterize the mobility of the deuterium on the surface, are extracted. For the interpretation of these data, parallel NMR studies of model g 2 -bound transition metal complexes are employed, which allow, owing to their simpler geometry and higher sensitivity, a quantitative modeling of the spin dynamics in the NMR experiment.