31P and195Pt solid state NMR spectra of anti-[(PHCy)ClPt(μ-PCy2)2Pt(PHCy)Cl] (3) and [(PHCy2)Pt(μ-PCy2)(κ2P,O-μ-POCy2)Pt(PHCy2)] (Pt-Pt) (4) were recorded under cross polarization/magic-angle spinning conditions (31P) or with the cross polarization/Carr-Purcell-Meiboom-Gill pulse sequence (195Pt) and compared to the data obtained by relativistic DFT calculations of31P and195Pt 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 of195Pt and31P nuclei between compounds 3 and 4 as mostly due to a change (in opposite directions for195Pt and31P) 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 to195Pt and31P shielding.
31P and195Pt solid-state NMR and DFT studies on platinum(i) and platinum(II) complexes / Todisco, Stefano; Saielli, Giacomo; Gallo, Vito; Latronico, Mario; Rizzuti, Antonino; Mastrorilli, Piero. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - STAMPA. - 47:27(2018), pp. 8884-8891. [10.1039/c8dt01561a]
31P and195Pt solid-state NMR and DFT studies on platinum(i) and platinum(II) complexes
Todisco, Stefano;Gallo, Vito;Latronico, Mario;Rizzuti, Antonino;Mastrorilli, Piero
2018-01-01
Abstract
31P and195Pt solid state NMR spectra of anti-[(PHCy)ClPt(μ-PCy2)2Pt(PHCy)Cl] (3) and [(PHCy2)Pt(μ-PCy2)(κ2P,O-μ-POCy2)Pt(PHCy2)] (Pt-Pt) (4) were recorded under cross polarization/magic-angle spinning conditions (31P) or with the cross polarization/Carr-Purcell-Meiboom-Gill pulse sequence (195Pt) and compared to the data obtained by relativistic DFT calculations of31P and195Pt 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 of195Pt and31P nuclei between compounds 3 and 4 as mostly due to a change (in opposite directions for195Pt and31P) 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 to195Pt and31P shielding.| File | Dimensione | Formato | |
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