Multinuclear solid-state NMR and DFT studies on phosphanido-bridged diplatinum complexes

Multinuclear (31P, 195Pt, 19F) solid-state NMR experiments on (nBu4N)2[(C6F5)2Pt(μ-PPh2)2Pt(C6F5)2] (1), [(C6F5)2Pt(μ-PPh2)2Pt(C6F5)2](Pt–Pt) (2), and cis-Pt(C6F5)2(PHPh2)2 (3) were carried out under cross-polarization/magic-angle-spinning conditions or with the cross-polarization/Carr–Purcell Meiboom–Gill pulse sequence. Analysis of the principal components of the 31P and 195Pt chemical shift (CS) tensors of 1 and 2 reveals that the variations observed comparing the isotropic chemical shifts of 1 and 2, commonly referred to as “ring effect”, are mainly due to changes in the principal components oriented along the direction perpendicular to the Pt2P2 plane. DFT calculations of 31P and 195Pt CS tensors confirmed the tensor orientation proposed from experimental data and symmetry arguments and revealed that the different values of the isotropic shieldings stem from differences in the paramagnetic and spin–orbit contributions.The Politecnico di Bari, the University of Padua, the University of Stuttgart, the Spanish MINECO/FEDER (Project No. CTQ2012-35251), and the Gobierno de Aragon (Grupo Consolidado E21: Quimica Inorganica y de los Compuestos Organometalicos) are gratefully acknowledged for financial support.Peer Reviewe