title: 63Cu-31P coupling constants and 63Cu quadrupole couplings from 31P CP/MAS spectra of copper (I)--phosphine complexes with aryldithiocarboxylates or benzoate.
abstract: Magic-angle spinning 31P NMR spectra of solid [CuS2C-Ph(PPh3)2] 1, [{CuS2C-pT}4(PPh3)2] 2, [{CuS2C-Ph}4(PPh3)2] 3. [CuS2C-Ph(dppm)]2 4 and [CuO2C-Ph(dppm)]2 5, (T = tolyl, dppm = bis(diphenylphosphino)methane) were obtained at 109.6 MH2. They consist of distorted quartets from non-equivalent phosphorus atoms and provide approximate values of the indirect spin-spin coupling constant J[63Cu,31P], that are indicative of the covalency of the dithiocarboxylate-copper bonding. The spacing distortions are related to a number of molecular and structural parameters and thereby allow an estimation of the copper quadrupole coupling constant e2qQ/h which, as expected, is smaller for tetra-coordinated (1, 2, 3 and 4) than for tri-coordinated (5) copper sites. The spectrum of 2 has been successfully simulated (including the isotope effects from the less abundant 65Cu isotope) using the full theory for calculation of the spin eigenfunctions of the quadrupolar nucleus.
authors.affiliation: Dipartimento di Scienze Chimiche, Università di Trieste, Italy.
authors.forename: F
authors.initials: F
authors.lastname: Asaro
authors.forename: A
authors.initials: A
authors.lastname: Camus
authors.forename: R
authors.initials: R
authors.lastname: Gobetto
authors.forename: A C
authors.initials: AC
authors.lastname: Olivieri
authors.forename: G
authors.initials: G
authors.lastname: Pellizer
mesh_terms: D001565:Benzoates / Q000737:chemistry*; D002614:Chelating Agents / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D010720:Phosphines / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013859:Thiocarbamates / Q000737:chemistry*
chemical_list: D001565:Benzoates; D002614:Chelating Agents; D010720:Phosphines; D013859:Thiocarbamates; D010758:Phosphorus; D003300:Copper; C044646:phosphine