title: BINOL-3,3'-triflone N,N-dimethyl phosphoramidites: through-space 19F,31P spin-spin coupling with a remarkable dependency on temperature and solvent internal pressure.
abstract: A combined computational and experimental study of the effects of solvent, temperature and stereochemistry on the magnitude of the through-space spin-spin coupling between 31P and 19F nuclei which are six-bonds apart is described. The reaction of 3-trifluoromethylsulfonyl-2,'2-dihydroxy-1,1'-binaphthalene (3-SO2CF3-BINOL) with hexamethylphosphorous triamide (P(NMe2)3) generates a pair of N,N-dimethylphosphoramidites which are diastereomeric due to their differing relative configurations at the stereogenic phosphorous centre and the axially chiral (atropisomeric) BINOL unit. Through-space NMR coupling of the 31P and 19F nuclei of the phosphoramidite and sulfone is detected in one diastereomer only. In the analogous N,N-dimethylphosphoramidite generated from 3,3'-(SO2CF3)2-BINOL only one of the diastereotopic trifluoromethylsulfone moieties couples with the 31P of the phosphoramidite. In both cases, the magnitude of the coupling is strongly modulated (up to 400 %) by solvent and temperature. A detailed DFT analysis of the response of the coupling to the orientation of the CF3 moiety with respect to the P-lone pair facilitates a confident assignment of the stereochemical identity of the pair of diastereomers. The analysis shows that the intriguing effects of environment on the magnitude of the coupling can be rationalised by a complex interplay of solvent internal pressure, molecular volume and thermal access to a wider conformational space. These phenomena suggest the possibility for the design of sensitive molecular probes for local environment that can be addressed via through-space NMR coupling.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol, UK.
authors.forename: Matthias
authors.initials: M
authors.lastname: Kruck
authors.forename: M Paz
authors.initials: MP
authors.lastname: Munoz
authors.forename: Hannah L
authors.initials: HL
authors.lastname: Bishop
authors.forename: Christopher G
authors.initials: CG
authors.lastname: Frost
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Chapman
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Köhn
authors.forename: Craig P
authors.initials: CP
authors.lastname: Butts
authors.forename: Guy C
authors.initials: GC
authors.lastname: Lloyd-Jones