31P and 195Pt solid-state NMR and DFT studies on platinum(i) and platinum(ii) complexes

Stefano Todisco; Giacomo Saielli; Vito Gallo; Mario Latronico; Antonino Rizzuti; Piero Mastrorilli

doi:10.1039/c8dt01561a

³¹P and ¹⁹⁵Pt solid-state NMR and DFT studies on platinum(i) and platinum(ii) complexes

Dalton Trans. 2018 Jul 10;47(27):8884-8891. doi: 10.1039/c8dt01561a.

Authors

Stefano Todisco¹, Giacomo Saielli, Vito Gallo, Mario Latronico, Antonino Rizzuti, Piero Mastrorilli

Affiliation

¹ Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, I-70125 Bari, Italy. p.mastrorilli@poliba.it.

PMID: 29845184
DOI: 10.1039/c8dt01561a

Abstract

31P and 195Pt 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 of 31P and 195Pt 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 195Pt and 31P nuclei between compounds 3 and 4 as mostly due to a change (in opposite directions for 195Pt and 31P) 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 195Pt and 31P shielding.