Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]VI Complex

As part of our interest in the photochemistry of platinum/p-block element complexes, we now report on the synthesis and photoreduction of [(Ph)­((o-Ph2P)­C6H4)2GePtCl3] (2-Ph), a complex featuring a tetravalent platinum center connected to a germyl ligand. When in the presence of a chlorine trap, 2-Ph undergoes a clean photolysis that affords [(Ph)­((o-Ph2P)­C6H4)2GePtCl] (1-Ph) and [(Cl)­((o-Ph2P)­C6H4)2GePtCl] (1-Cl) as confirmed by NMR spectroscopy. While the formation of 1-Ph results from the elimination of a chlorine equivalent from 2-Ph, the formation of 1-Cl indicates chlorobenzene elimination, which was confirmed and quantified using GC-MS. These results provide a unique example of a germanium-centered light-induced reduction process resulting in the ipso-chlorination of a phenyl-germanium species.