title: A multinuclear solid-state NMR study of alkali metal ions in tetraphenylborate salts, M[BPh4] (M = Na, K, Rb and Cs): what is the NMR signature of cation-pi interactions?
abstract: We report a multinuclear solid-state ( (23)Na, (39)K, (87)Rb, (133)Cs) NMR study of tetraphenylborate salts, M[BPh 4] (M = Na, K, Rb, Cs). These compounds are isostructural in the solid state with the alkali metal ion surrounded by four phenyl groups resulting in strong cation-pi interactions. From analyses of solid-state NMR spectra obtained under stationary and magic-angle spinning (MAS) conditions at 11.75 and 21.15 T, we have obtained the quadrupole coupling constants, C Q, and the chemical shift tensor parameters for the alkali metal ions in these compounds. We found that the observed quadrupole coupling constant for M (+) in M[BPh 4] is determined by a combination of nuclear quadrupole moment, Sternheimer antishielding factor, and unit cell dimensions. On the basis of a comparison between computed paramagnetic and diamagnetic contributions to the total chemical shielding values for commonly found cation-ligand interactions, we conclude that cation-pi interactions give rise to significantly lower paramagnetic shielding contributions than other cation-ligand interactions. As a result, highly negative chemical shifts are expected to be the NMR signature for cations interacting exclusively with pi systems.
authors.affiliation: Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6. gang.wu@chem.queensu.ca
authors.forename: Gang
authors.initials: G
authors.lastname: Wu
authors.forename: Victor
authors.initials: V
authors.lastname: Terskikh
mesh_terms: D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D007477:Ions / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D008672:Metals, Alkali / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D012015:Reference Standards; D012492:Salts / Q000737:chemistry; D013775:Tetraphenylborate / Q000737:chemistry*
chemical_list: D002412:Cations; D007477:Ions; D008672:Metals, Alkali; D009942:Organometallic Compounds; D012492:Salts; D013775:Tetraphenylborate