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Author ORCID ID is 0000000295171704
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  1. In this work, we utilize direct 17O DNP for the characterization of non-protonated oxygens in heterogeneous catalysts. The optimal sample preparation and population transfer approach for 17O direct DNP experiments performed on silica surfaces is determined and applied to the characterization of Zr- and Y-based mesoporous silica-supported single-site catalysts.
  2. Homoleptic tris(alkyl) rare earth complexes Ln{C(SiHMe 2) 3} 3 (Ln = La, 1a; Ce, 1b; Pr, 1c; Nd, 1d) are synthesized in high yield from LnI 3THF n and 3 equiv of KC(SiHMe 2) 3. X-ray diffraction studies reveal 1a–d are isostructural, pseudo-C 3-symmetric molecules that contain two secondary Ln←HSi interactions per alkyl ligand (six total). Spectroscopic assignments are supported by comparison with Ln{C(SiDMe 2) 3} 3 and DFT calculations. Here, the Ln←HSi and terminal SiH exchange rapidly on the NMR time scale at room temperature, but the two motifs are resolved at low temperature. Variable-temperature NMR studies provide activationmore » parameters for the exchange process in 1a (ΔH = 8.2(4) kcal·mol –1; ΔS = –1(2) cal·mol –1K –1) and 1a-d 9 (ΔH = 7.7(3) kcal·mol –1; ΔS = –4(2) cal·mol –1K –1). Comparisons of lineshapes, rate constants (kH/kD), and slopes of ln(k/T) vs 1/T plots for 1a and 1a-d 9 reveal that an inverse isotope effect dominates at low temperature. DFT calculations identify four low-energy intermediates containing five β-Si–H→Ln and one γ-C–H→Ln. The calculations also suggest the pathway for Ln←HSi/SiH exchange involves rotation of a single C(SiHMe 2) 3 ligand that is coordinated to the Ln center through the Ln–C bond and one secondary interaction. These robust organometallic compounds persist in solution and in the solid state up to 80 °C, providing potential for their use in a range of synthetic applications. For example, reactions of Ln{C(SiHMe 2) 3} 3 and ancillary proligands, such as bis-1,1-(4,4-dimethyl-2-oxazolinyl)ethane (HMeC(Ox Me2) 2) give {MeC(Ox Me2) 2}Ln{C(SiHMe 2) 3} 2, and reactions with disilazanes provide solvent-free lanthanoid tris(disilazides).« less
  3. To MCoMe reacts rapidly with CO to give a low spin To MCo{C(O)Me}CO species, which is selectively oxygenated to form To MCoOAc.
  4. Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radicalmore » distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.« less
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  5. A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds Ln{N(SiHMe 2) tBu} 3 (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1–3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln←H–Si interactions. These features are retained in solvent-coordinated 2·Et 2O, 2·THF, and 3·THF. The change in spectroscopic features characterizing the secondary interactions (ν SiH, 1 J SiH) from the unactivated SiH in the silazane HN(SiHMe 2) tBumore » follows the trend 3 > 2 > 1 ≈ 2·Et 2O > 2·THF ≈ 3·THF. Ligand lability follows the same pattern, with Et 2O readily dissociating from 2·Et 2O while THF is displaced only during surface grafting reactions. 1 and 2·THF graft onto mesoporous silica nanoparticles (MSN) to give Ln{N(SiHMe 2) tBu} n@MSN (Ln = Sc (1@MSN), Y (2@MSN)) along with THF and protonated silazido as HN(SiHMe 2) tBu and H 2N tBu. The surface species are characterized by multinuclear and multidimensional solid-state (SS) NMR spectroscopic techniques, as well as diffuse reflectance FTIR, elemental analysis, and reaction stoichiometry. A key 1 J SiH SSNMR measurement reveals that the grafted sites most closely resemble Ln·THF adducts, suggesting that siloxane coordination occurs in grafted compounds. These species catalyze the hydroamination/bicyclization of aminodialkenes, and both solution-phase and interfacial conditions provide the bicyclized product with equivalent cis:trans ratios. As a result, similar diastereoselectivities mediated by catalytic sites under the two conditions suggest similar effective environments.« less

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