Solid-state NMR of quadrupolar nuclei for investigations into supported organometallic catalysts: scope and frontiers.

The rational development of heterogeneous catalysts is a prerequisite for improving current catalytic technologies. One of the most successful approaches to achieve this goal is the grafting of organometallic complexes onto a given support, via surface organometallic chemistry (SOMC). In such cases, the immobilization of (transition) metal centres onto an inorganic support affords single-site catalysts with precise tuning of the coordination sphere and thus target-specific catalytic reactivity. In this context, the precise characterization of the surface sites by several spectroscopic techniques in parallel is of paramount importance. Solid-state NMR, in particular for half-integer quadrupolar nuclei, is a method that has increased its scope in the field of catalysis, especially due to recent methodological breakthroughs, occasionally combined with DFT calculations. In this tutorial review, we provide an overview of the most robust and efficient NMR experiments for half-integer quadrupolar nuclei, from simple one-dimensional acquisition under static and MAS conditions up to high-resolution and heteronuclear correlation two-dimensional spectra, as illustrated by selected examples.

17O MAS NMR studies of oxo-based olefin metathesis catalysts: a critical assessment of signal enhancement methods.

The DFS enhancement method as applied to 17O MAS NMR was critically assessed, first on NaPO3, a simple binary glass system, and in a second step, on a series of catalysis-related organometallic molecules and materials. The robustness of DFS was investigated for the wide range of anisotropic parameters (quadrupolar coupling and chemical shift anisotropy) encountered in these samples. Emphasis has been put on the variation of signal enhancements with respect to the DFS final sweep frequency, pulse amplitude and pulse duration, while line shape distortion issues were also addressed. Finally, the robustness of DFS enhancement of the 17O MAS NMR signal is shown through its successful application to silica-supported olefin metathesis catalysts.

Labile degree of disorder in bismuth-oxophosphate compounds: illustration through three new structural types.

Here, we analyze the crystal structures of three new Bi/M oxophosphates, focusing on the ambiguity between order and disorder in different structural subunits. The three structures are original but systematically built on the assembly of O(Bi,M)4 tetrahedra into various 1D-oxocenterd units, separated by PO4 groups that create cationic channels. Two main subunits show versatile degrees of disorder, i.e., the cationic channels and some of the terminal O(Bi,M)4 entities. (a) In the compound [Bi2(Bi1.56K0.44)(dis)O3]K0.88(dis)(PO4)2, the K/K and K/Bi disorder is total on both nano- and micro-sized domains. (b) In the incommensurately modulated [Bi10(Bi∼0.5Cd∼0.5)8(dis)O16](Bi0.6Cd0.8)2(ord)(PO4)8, only the cationic channels show an ordered Bi/Cd arrangement which can be modified by minor stoichiometric changes between domains. (c) In [Bi18Zn10O21](ord)Zn5(ord)(PO4)14, both subunits are almost perfectly ordered (complex Bi/Zn sequence) into a 7-fold supercell, but this order strongly depends on the observation scale and is mainly lost in micronic-grains also due to slight compositional changes. However, the refined noncentrosymmetric organization is maintained (SHG tests) in the bulk. The relative stability of ordered versus disordered sites is discussed on the basis of the existence of two possible mixed sites and probably depends on the M chemical nature. Disorder was characterized by use of solid-state (31)P NMR probing for the first two cases. Finally, the observed disordered or long periodicities along the infinite dimension suggest the sketch of a periodic/rigid skeleton of O(Bi,M)4 units with counterions filling the interspace in more or less disordered arrangements.

Structure of Nb2O5-NaPO3 glasses by X-ray and neutron diffraction.

X-ray and neutron diffraction of excellent resolving power are used to determine the atomic structure of niobium phosphate glasses. These studies complement the results of earlier (31)P and (93)Nb nuclear magnetic resonance, Raman scattering and O1s X-ray photoelectron spectroscopy of the (Nb2O5)x-(NaPO3)(1-x) glasses (0 ≤ x ≤ 0.40). The Nb-O distances behave uniformly for glasses of 0.08 ≤ x ≤ 0.20 with distorted NbO6 octahedra that are characterized by a corner with a short Nb-O bond of 0.174 nm, four bonds of ~0.20 nm and a longer bond. The concomitant change of PO4 units from chain to end groups extends likewise to glasses of x = ~0.20, i.e. only one O atom per Nb contributes to the rupture of phosphate chains. This behaviour differs from that of related crystal structures and phosphate glasses of other oxide additions. Asymmetric Nb-O-Nb bridges that include the short Nb-O bond are formed for glasses of x ≤ 0.20 while symmetric bridges with two Nb-O bonds of ~0.190 nm appear for x > 0.2. A pre-peak at 8 nm(-1) is found in the S(Q) for glasses of 0.08 ≤ x ≤ 0.20 which is interpreted as the presence of niobate and sodium phosphate micro-domains. The weakness of this pre-peak if it is compared with that of similar GeO2-KPO3 glasses is explained with modifications of the micro-domain structure by a fraction of non-bridging O in Nb-O···Na(+) sites. The pre-peak vanishes for the glass of x = 0.40.

On the use of 17O NMR for understanding molecular and silica-grafted tungsten oxo siloxide complexes.

17O-labelled tungsten siloxide complexes [WOCl2(OSitBu3)2] (1-Cl) and [WOMe2(OSitBu3)2] (1-Me) were prepared and characterized by 17O MAS NMR, with input from theoretical calculations of NMR parameters. Guidelines linking 17O NMR parameters and the coordination sphere of molecular and silica-grafted tungsten oxo species are proposed. The grafting of 1-Me on SiO2-700 afforded material 2, with surface species [(SiO)WOMe2(OSitBu3)] as shown by elemental analysis, IR and 1H and 13C MAS NMR. The DFT calculations of the grafting mechanism are in line with the observed reactivity. They indicate the occurrence of several isomeric species of close energy for the grafted W centers, precluding efficient 17O MAS NMR studies. The lack of catalytic activity in olefin metathesis and ring-opening olefin metathesis polymerization indicates that initiation by α-H elimination is not operative in 2, contrary to related tungsten surface species, which illustrates the crucial influence of the nature of the metal coordination sphere.

Observation of proximities between spin-1/2 and quadrupolar nuclei: which heteronuclear dipolar recoupling method is preferable?

We have recently shown that the dipolar-mediated heteronuclear multiple-quantum coherence (D-HMQC) method allows observing through-space proximities between spin-1/2 ((1)H, (13)C, (31)P...) and quadrupolar ((23)Na, (27)Al...) nuclei. However, the D-HMQC effectiveness depends on the choice of the heteronuclear dipolar recoupling sequence. Here, we compare the efficiency and the robustness of four rotor-synchronized sequences: the symmetry-based ones, R4(1)(2)R4(1)(-2) and its super-cycled version, SR4(1)(2), and two schemes based on simultaneous amplitude and frequency modulations, denoted SFAM-1 and SFAM-2. For the SFAM methods, we point out efficient recoupling conditions that facilitate their experimental optimization and we introduce analytical expressions for the buildup of D-HMQC signal in the case of an isolated spin pair. We show that the main differences between these four sequences lie in the number of adjustable parameters and in their robustness with respect to chemical shift and homonuclear dipolar interactions. The relative performances of these four recoupling sequences are analyzed using average Hamiltonian theory, numerical simulations, and (27)Al-{(31)P} D-HMQC experiments on crystalline aluminophosphate.

Structural characterisation of phosphate materials: new insights into the spatial proximities between phosphorus and quadrupolar nuclei using the D-HMQC MAS NMR technique.

We show in this article how the spatial proximity between phosphorus and quadrupolar nuclei can be efficiently and easily investigated with the D-HMQC (Dipolar Hetero-nuclear Multiple-Quantum Coherences) NMR technique. Compared to the commonly used CP-HETCOR (Cross-Polarisation HETero-nuclear CORrelation) sequence, the D-HMQC pulse scheme exhibits a higher sensitivity and a better robustness with respect to spinning frequency, electronic shielding and quadrupole interaction, and thus does not require time-consuming and complicated optimisation procedures. The advantages of the D-HMQC are demonstrated in this article through the acquisition of (31)P/S through-space two-dimensional correlation NMR spectra providing unreported structural information on (i) a sodium alumino-silicate glass doped with only 3% of P(2)O(5), (ii) a potassium boro-phosphate glass containing BO(3) and BO(4) groups and (iii) a crystalline zirconium vanado-phosphate. All these systems, representative of the most important mixed phosphate network materials, cannot be correctly investigated with the conventional CP-HETCOR NMR technique.

Heteronuclear dipolar decoupling effects on multiple-quantum and satellite-transition magic-angle spinning NMR spectra.

We here report on the influence of heteronuclear dipolar decoupling on the (27)Al 3QMAS, 5QMAS, and the double-quantum filter-satellite-transition magic-angle spinning (DQF-STMAS) spectra of a strongly dipolar-coupled system, gibbsite. The requirements for heteronuclear dipolar decoupling increase with the order of coherence evolving in the indirect dimension of a two-dimensional (2D) experiment. The isotropic line width of the high-resolution 2D spectra, in samples like gibbsite, is composed of four parts: the distribution of isotropic shifts (delta(ISO), delta(QIS)), the homogeneous broadening related to the proton-proton flip-flop terms, the (27)Al-(27)Al homonulcear dipolar couplings, and the (1)H-(27)Al heteronuclear dipolar couplings. It is shown that, even in the case of gibbsite, where a strong proton-proton bath exists, the main resolution limiting factor in these experiments resides in the (1)H-(27)Al dipolar interaction.

Resolution enhancement using a new multiple-pulse decoupling sequence for quadrupolar nuclei.

A new decoupling composite pulse sequence is proposed to remove the broadening on spin S=1/2 magic-angle spinning (MAS) spectra arising from the scalar coupling with a quadrupolar nucleus I. It is illustrated on the (31)P spectrum of an aluminophosphate, AlPO(4)-14, which is broadened by the presence of (27)Al/(31)P scalar couplings. The multiple-pulse (MP) sequence has the advantage over the continuous wave (CW) irradiation to efficiently annul the scalar dephasing without reintroducing the dipolar interaction. The MP decoupling sequence is first described in a rotor-synchronised version (RS-MP) where one parameter only needs to be adjusted. It clearly avoids the dipolar recoupling in order to achieve a better resolution than using the CW sequence. In a second improved version, the MP sequence is experimentally studied in the vicinity of the perfect rotor-synchronised conditions. The linewidth at half maximum (FWHM) of 65 Hz using (27)Al CW decoupling decreases to 48 Hz with RS-MP decoupling and to 30 Hz with rotor-asynchronised MP (RA-MP) decoupling. The main phenomena are explained using both experimental results and numerical simulations.

On the use of solid-state 45Sc NMR for structural investigations of molecular and silica-supported scandium amide catalysts.

Tris- and tetra-coordinated scandium amides were grafted onto silica and probed as catalysts for alkyne dimerization. 45Sc NMR was carried out, providing information about the metal coordination sphere. The increasing number of coordinated ligands was correlated with decreased catalytic activity.

Preparation of monopodal and bipodal aluminum surface species by selective protonolysis of highly reactive [AlH3(NMe2Et)] on silica.

The synthesis and characterization of silica-grafted monopodal and bipodal aluminum hydrides has been achieved starting from 200 °C- and 700 °C-annealed silica and [AlH3(NMe2Et)]. The mechanism by which aluminum trishydride reacts with isolated and vicinal silanols, assisted by the amine, has been investigated computationally at the ωB97XD-DFT level.

Implementing SPAM into STMAS: a net sensitivity improvement in high-resolution NMR of quadrupolar nuclei.

Gan and Kwak recently introduced two new tools for high-resolution 2D NMR methods applied to quadrupolar nuclei: double-quantum filtering in STMAS (DQF-STMAS) and the soft-pulse added mixing (SPAM) idea. Double-quantum filtering suppresses all undesired signals in the STMAS method with limited loss in sensitivity. With SPAM, all pathways are added constructively after the second hard-pulse instead of using a single pathway as previously. Here, the sensitivity, advantages and drawbacks of DQF-STMAS are compared to 3QMAS. Additionally, SPAM can be included into DQF-STMAS method, resulting in a net sensitivity gain with respect to 3QMAS of ca. 10-15.

Increasing the sensitivity of 2D high-resolution NMR methods applied to quadrupolar nuclei.

Gan and Kwak recently proposed a soft-pulse added mixing (SPAM) idea in the classical two-pulse multiple-quantum magic-angle spinning scheme. In the SPAM method, a soft pi/2 pulse is added after the second hard-pulse (conversion pulse) and all coherence orders in between them are constructively used to obtain the signal. We, here, further extend this idea to distributed samples where the signal mainly results from echo pathways and that from anti-echo pathways dies out after a few t1 increments. We show that, with a combination of SPAM and collection of fewer anti-echoes, an enhancement of the signal to noise ratio by a factor of ca. 3 may be obtained over the z-filtered version. This may prove to be useful even for samples with long T2' relaxation times.

Direct evidence of Lowenstein's rule violation in swelling high-charge micas.

The structure of high-charged micas, Na-n-micas (n = 2 and 4), a family of synthetic silicates with a wide range of applications, was investigated through the use of (17)O solid-state NMR at natural abundance in order to preserve quantitative spectral information. The use of a very high-field and highly sensitive probehead, together with (17)O NMR literature data allowed for the detection of an isolated signal at 26 ppm, assigned partially to AlOAl, as evidence of the violation of Lowenstein's rule for Na-4-mica.

Double-quantum NMR spectroscopy of 31P species submitted to very large CSAs.

We introduce an original pulse sequence, BR2(2)(1)(taupitau), which is a block super-cycled R2(2)(1) sequence employing as basic element a pi pulse sandwiched by 'window' intervals. This homonuclear dipolar recoupling method allows the efficient excitation of double-quantum coherences between spin-1/2 nuclei submitted to very large chemical shift anisotropy. We demonstrate that this technique can be employed in double-quantum<-->single-quantum (31)P homonuclear correlation experiment at high magnetic field (B(0)>or=14 T) and high MAS frequencies (nu(R)>or=30 kHz). The performances of BR2(2)(1)(taupitau) are compared to those of the double-quantum recoupling methods, such as BABA and bracketed fp-RFDR, which were already employed at fast MAS rates. The BR2(2)(1)(taupitau) sequence displays a higher robustness to CSA and offset than the other existing techniques.

Correlation NMR spectroscopy involving quadrupolar nuclei.

We review the recent developments proposed for integer or half-integer quadrupolar nuclei, focussing on the methods to observe them under high-resolution and to analyze their through-space and through-bond connectivities.

93Nb and 17O NMR chemical shifts of niobiophosphate compounds.

Niobiophosphate compounds with a large range of niobium and oxygen environments were studied with (93)Nb and (17)O solid-state NMR. (93)Nb isotropic chemical shift of pure niobate Nb(ONb)(6), pure phosphate Nb(OP)(6) and mixed phosphate-niobate Nb(OP)(x)(ONb)((6-x)) (1

Location of protons in anhydrous Keggin heteropolyacids H(3)PMo(12)O(40) and H(3)PW(12)O(40) by (1)H[(31)P]/(31)P[(1)H] REDOR NMR and DFT quantum chemical calculations.

HeteroPolyAcids (HPA's) are a class of solid acids that have broad applications in many fields of science and technology, including catalysis and chemical engineering. The proton locations within the thermally stable and commonly known Keggin unit, which is the primary structure building unit/block, has remained undetermined in anhydrous HPAs, despite numerous theoretical and experimental efforts. However, Rotational Echo DOuble Resonance (REDOR) NMR and Density Functional Theory (DFT) quantum chemical calculations offer a new opportunity to determine the exact locations of protons within the Keggin unit. The crucial experimental evidence is provided for the basic and very extensively studied acidic form of H(8-n)X(n+)M(12)O(40), X = Si, P and M = Mo, W, belonging to the Keggin structure. While showing that the acidic protons are located in the bridging oxygen positions (R(P-H) = 520 +/- 20 pm) in H(3)PMo(12)O(40) and in the terminal oxygen positions (R(P-H) = 570 +/- 20 pm) in H(3)PW(12)O(40), REDOR measurements also provide for the first time the structural basis to consistently rank the acid strength for the important class of Keggin solid catalysts.