title: Measurement of delta(1)J((199)Hg, (31)P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury-phosphorus coupling tensors.
abstract: Using 31P solid-state NMR spectroscopy, anisotropy in the indirect 199Hg-31P spin-spin coupling tensor (DeltaJ) for powdered [HgPCy3(OAc)2]2 (1) has been measured as 4700 +/- 300 Hz. Zeroth-order regular approximation (ZORA) density functional theory (DFT) calculations, including scalar and spin-orbit relativistic effects, performed on 1 and a series of other related compounds show that DeltaJ(199Hg, (31)P) arises entirely from the ZORA Fermi-contact-spin-dipolar cross term. The calculations validate assumptions made in the spectral analysis of 1 and in previous determinations of DeltaJ in powder samples, namely that J is axially symmetric and shares its principal axis system with the direct dipolar coupling tensor (D). Agreement between experiment and theory for various 199Hg, 31P spin-spin coupling anisotropies is reasonable; however, experimental values of 1J(199Hg, 31P)(iso) are significantly underestimated by the calculations. The most important improvements in the agreement were obtained as a result of including more of the crystal lattice in the model used for the calculations, e.g., a change of 43% was noted for 1J(199Hg, 31P)(iso) in [HgPPh3(NO3)2]2 depending on whether the two or three nearest nitrate ions are included in the model. Finally, we have written a computer program to simulate the effects of non-axial symmetry in J and of non-coincidence of the J and D on powder NMR spectra. Simulations clearly show that both of these effects have a pronounced impact on the 31P NMR spectrum of 199Hg-31P spin pairs, suggesting that the effects should be observable experimentally if a suitable compound can be identified.
authors.affiliation: Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario, Canada K1N6N5. dbryce@uottawa.ca
authors.forename: David L
authors.initials: DL
authors.lastname: Bryce
authors.forename: Noémie Manuelle Dorval
authors.initials: NM
authors.lastname: Courchesne
authors.forename: Frédéric A
authors.initials: FA
authors.lastname: Perras
mesh_terms: D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009941:Organomercury Compounds / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D011789:Quantum Theory; D015203:Reproducibility of Results
chemical_list: D009941:Organomercury Compounds; D010758:Phosphorus