New organoplatinum(II) complexes [PtR 2 (PN)] (PN = 2-(diphenylphosphinoamino)pyridine, R = Me, 1a, or p-MeC 6 H 4 , 1b) were synthesized by the reaction of [Pt(p-MeC 6 H 4 ) 2 (SMe 2 ) 2 ] or [Me 2 Pt(m-SMe 2 ) 2 PtMe 2 ] with 1 and 2 equiv. of PN, respectively. The reaction of Pt(II) complexes 1 with MeI gave the Pt(IV) complexes [PtR 2 (PN)MeI] (R = Me; 2a, and p-MeC 6 H 4 ; 2b). All the complexes were fully characterized using multinuclear ( 1 H, 31 P, 13 C, and 195 Pt) NMR spectroscopy. Density functional theory calculations have been performed to find approximate structures for all described complexes. The platinum(II) complexes have a 5d p (Pt)-p*(PN) metal-to-ligand charge-transfer band, which was used to easily follow the kinetics of their reactions with MeI. The classical S N 2 mechanism was suggested. The rates of the reactions at different temperatures were measured and were consistent with the proposed mechanism, large negative DS z values were found in each reaction. The PN chelating complexes [PtR 2 (PN)], 1, reacted almost 100 or 300 times slower with MeI as compared to that of the NN chelating complex [PtR 2 (bpy)] (bpy = 2,2 0 -bipyridine) in acetone or benzene, respectively. This was attributed to the p-acceptance through the P ligating atom of PN ligand, which decreases the electron density of Pt(II) in PN chelating complexes.

Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o‐(Ph2P)C6H4)2GeIVCl2]PtIICl2 and [(o‐(Ph2P)C6H4)2ClGeIII]PtIIICl3, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o‐(Ph2P)C6H4)2ClGeIII]PtICl with quantum yields of 1.7 % and 3.2 % for the GeIV–PtII and GeIII–PtIII isomers, respectively. Conversion of the GeIV–PtII isomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the GeIII–PtIII isomer point to a ligand arene–Cl. charge‐transfer complex as an intermediate.

Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o‐(Ph2P)C6H4)2GeIVCl2]PtIICl2 and [(o‐(Ph2P)C6H4)2ClGeIII]PtIIICl3, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o‐(Ph2P)C6H4)2ClGeIII]PtICl with quantum yields of 1.7 % and 3.2 % for the GeIV–PtII and GeIII–PtIII isomers, respectively. Conversion of the GeIV–PtII isomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the GeIII–PtIII isomer point to a ligand arene–Cl. charge‐transfer complex as an intermediate.