Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts

Autor(es)

Wuebker, Anna-Lena ^[1] ; Koppe, Jonas ^[1] ; Bradtmueller, Henrik ^{[1, 2]} ; Keweloh, Lukas ^[3] ; Pleschka, Damian ^[3] ; Uhl, Werner ^[3] ; Hansen, Michael Ryan ^[1] ; Eckert, Hellmut ^{[4, 1]}

Afiliação do(s) autor(es)

^[1] WWU Munster, Inst Phys Chem, Corrensstr 28-30, D-48149 Munster - Germany

^[2] Univ Fed Sao Carlos, Vitreous Mat Lab, Dept Mat Engn, CP 676, BR-13565905 Sao Carlos, SP - Brazil

^[3] WWU Munster, Inst Anorgan & Analyt Chem, Corrensstr 28-30, D-48149 Munster - Germany

^[4] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13566590 Sao Carlos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRY-A EUROPEAN JOURNAL; v. 27, n. 52 AUG 2021.
• Citações Web of Science: 0

Resumo

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alane-phosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect Al-27-P-31 spin-spin coupling constants, and Al-27 nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the P-31 NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The Al-27 NMR central transition signals are spread out over a broad frequency range (>200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static Al-27 wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. Al-27 chemical shifts and quadrupole tensor components offer a facile and clear distinction between three- and four-coordinate aluminum environments. For measuring internuclear Al...P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al...P distances in these compounds can be measured within a precision of +/- 0.1 angstrom. (AU)

• Processo FAPESP: 13/07793-6 - CEPIV - Centro de Ensino, Pesquisa e Inovação em Vidros
• Beneficiário: Edgar Dutra Zanotto
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 19/26399-3 - Elucidação de rearranjos estruturais durante o processo de relaxação e cristalização de materiais vítreos
• Beneficiário: Henrik Bradtmüller
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado