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Structural Characterization of Frustrated Lewis Pairs and Their Reaction Products Using Modern Solid‐State NMR Spectroscopy Techniques
Author(s) -
Wiegand Thomas,
Siedow Melanie,
Eckert Hellmut,
Kehr Gerald,
Erker Gerhard
Publication year - 2015
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201400149
Subject(s) - chemistry , frustrated lewis pair , borane , intramolecular force , reactivity (psychology) , boranes , catalysis , nuclear magnetic resonance spectroscopy , characterization (materials science) , boron , computational chemistry , adduct , molecule , spectroscopy , lewis acids and bases , chemical shift , dipole , chemical physics , crystallography , stereochemistry , organic chemistry , nanotechnology , materials science , alternative medicine , medicine , pathology , physics , quantum mechanics
Frustrated Lewis pair (FLP) chemistry has provided a new strategy for small‐molecule binding and/or catalytic activation. The most prominent FLPs are based on intramolecular phosphaneborane adducts, the catalytic properties of which can be tailored over wide ranges of reactivity and selectivity. Advanced solid‐state NMR spectroscopic techniques, together with DFT calculations, can provide new structural insights in these systems. This review illustrates the utility of 31 P and 11 B NMR chemical shifts, 11 B electric field gradient tensors, and 31 P 11 B indirect and direct dipoledipole interactions for characterizing intramolecular boranephosphane FLPs. We demonstrate the potential of this method to 1) quantify the extent of boronphosphorus bonding interactions (and hence, the “degree of frustration”); 2) reveal specific structural details (i.e., boronphosphorus distances and other local geometric aspects) related to their catalytic activities; and (3) characterize products of FLP reactions with regard to molecular structure, stereochemistry, and aggregation properties in terms of internuclear distances, bonding connectivities, and orientational parameters.