Solid-state NMR strategies for the structural characterization of paramagnetic NO adducts of Frustrated Lewis Pairs (FLPs)

By N,N addition of NO to the norbonane annulated borane-phosphane Frustrated Lewis pair (FLP) 1 a five-membered heterocyclic persistent aminoxyl radical 2 and its diamagnetic hydroxylamine reduction product 3 are prepared, and the comprehensive multinuclear solid state NMR characterization (H-1, B-11, F-19, P-31) of these FLP adducts is reported. Signal quantification experiments using a standard addition method reveal that the B-11 and P-31 NMR signals observed in 2 actually arise from molecular impurities of 3 embedded in the paramagnetic crystal. In contrast analogous quantification experiments reveal that the H-1 and F-19 MAS-NMR spectra originate from spin-carrying molecules. Peak assignments are based on DFT-calculated Mulliken spin densities, which lead to the surprising result that the largest paramagnetic shift affecting a proton NMR resonance in 2 originates from intermolecular interactions. For the F-19 nuclei, experiments and calculations indicate that paramagnetic shift effects are very small. In this case, assignments are based on DFT chemical shift calculations carried out on diamagnetic 3 and F-19(B-11) Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) experiments. The set of experiments described here defines an efficient strategy for the structural analysis of paramagnetic FLP adducts. (C) 2014 Elsevier Inc. All rights reserved.