31P and 195Pt solid-state NMR and DFT studies on platinum(i) and platinum(ii) complexes. Issue 27 (30th May 2018)

• Record Type: Journal Article
• Authors: Todisco, Stefano; Saielli, Giacomo; Gallo, Vito; Latronico, Mario; Rizzuti, Antonino; Mastrorilli, Piero
• Is Part Of: Dalton transactions. Volume 47:Issue 27(2018)
• Page Start: 8884
• Page End: 8891
• Publication Date: 2018-05-30
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt01561a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : 31 P and 195 Pt solid state NMR spectra on anti -[(PHCy)ClPt(μ-PCy2 )2 Pt(PHCy)Cl] (3 ) and [(PHCy2 )Pt(μ-PCy2 )(κ 2 P, O-μ-POCy2 )Pt(PHCy2 )] (Pt–Pt) (4 ) were recorded under CP/MAS conditions ( 31 P) or with the CP/CPMG pulse sequence ( 195 Pt) and compared to data obtained by relativistic DFT calculations of 31 P and 195 Pt CS tensors and isotropic shielding at the ZORA Spin Orbit level. Abstract : 31 P and 195 Pt solid state NMR spectra of anti -[(PHCy)ClPt(μ-PCy2 )2 Pt(PHCy)Cl] (3 ) and [(PHCy2 )Pt(μ-PCy2 )(κ 2 P, O-μ-POCy2 )Pt(PHCy2 )] (Pt–Pt) (4 ) were recorded under cross polarization/magic-angle spinning conditions ( 31 P) or with the cross polarization/Carr–Purcell–Meiboom–Gill pulse sequence ( 195 Pt) and compared to the data obtained by relativistic DFT calculations of 31 P and 195 Pt CS tensors and isotropic shielding at the ZORA spin–orbit level. A good agreement with the experimental results was found and it was possible to rationalize the chemical shift differences of 195 Pt and 31 P nuclei between compounds3 and4 as mostly due to a change (in opposite directions for 195 Pt and 31 P) of the principal component of the shielding tensor perpendicular to the molecular plane defined by the Pt and P atoms. Paramagnetic and spin–orbit terms were found to be the most important contributions to 195 Pt and 31 P shielding.