title: Investigating Unusual Homonuclear Intermolecular "Through-Space" J Couplings in Organochalcogen Systems.
abstract: Although the electron-mediated spin-spin or J coupling is conventionally viewed as transmitted via covalent bonds, examples of J couplings between atoms that are not formally bonded but are in close proximity (termed "through-space" J couplings) have been reported. In this work, we investigate the observation of homonuclear31P J couplings in organochalcogen heterocycles, which occur between31P in two separate molecules, confirming without doubt their through-space nature. The presence of this interaction is even more surprising for one compound, where it occurs between crystallographically equivalent species. Although crystallographically equivalent species need not be magnetically equivalent in the solid state, owing to the presence of anisotropic interactions, we demonstrate that it is not the shielding anisotropy that lifts magnetic equivalence, in this case, but the presence of heteronuclear couplings to77Se. We support our experimental observations with periodic scalar-relativistic density functional theory calculations and coupling density deformation plots to visualize the mechanism of these interesting interactions.
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: Paula
authors.initials: P
authors.lastname: Sanz Camacho
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: David
authors.initials: D
authors.lastname: McKay
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Dawson
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: Christin
authors.initials: C
authors.lastname: Kirst
authors.affiliation: Department of Materials, University of Oxford , Oxford OX1 3PH, U.K.
authors.forename: Jonathan R
authors.initials: JR
authors.lastname: Yates
authors.affiliation: Department of Materials, University of Oxford , Oxford OX1 3PH, U.K.
authors.forename: Timothy F G
authors.initials: TF
authors.lastname: Green
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: David B
authors.initials: DB
authors.lastname: Cordes
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: J Derek
authors.initials: JD
authors.lastname: Woollins
authors.affiliation: School of Chemistry, EaStCHEM and Centre of Magnetic Resonance, University of St Andrews , St Andrews, Fife KY16 9ST, U.K.
authors.forename: Sharon E
authors.initials: SE
authors.lastname: Ashbrook