Transition metal halides in high oxidation states, such as platinum (IV) chlorides are prone to two-electron photoreduction events. In recent years, a similar behavior has been discovered for bimetallic Pt/E (E=main group element) complexes that undergo reductive elimination of chlorine equivalents. The photo-reactivity of these compounds is usually explained by population of the Pt-Cl antibonding orbitals in the excited state. However, it has often been unclear whether Cl dissociation takes place exclusively from the platinum center or whether the photoinduced cleavage of E-X bonds (X = anionic ligand) also contributes to the photoreduction reaction. To address this question, we have now prepared a series of bimetallic Ge/Pt species, including one featuring a germanium-bound phenyl group. Our results point to the direct involvement of the Ge-Ph in the photoreduction process, with chlorobenzene unambiguously identified as a product of this reaction.

Photoreductive elimination of chlorobenzene from a bimetallic Ge/Pt complex

ACS Spring Meeting 2021

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