Nucleophilic Reactions of Osmanaphthalynes with PMe3 and H2O

Members of a new class of complexes, 2(CF3), 2(H), 2(Br), 2(I), and 2(OCH3), have been synthesized in a one-pot method involving the treatment of osmanaphthalynes bearing corresponding substituents (1(CF3), 1(H), 1(Br), 1(I), and 1(OCH3)) with trimethylphosphine (PMe3) and water. The main reaction process involves two steps, namely a ligand-exchange with trimethylphosphine and nucleophilic addition of water to the Os equivalent to C bond of the osmanaphthalyne. The substituents have a significant influence on the rate of the reaction, as befits a nucleophilic addition. Fortunately, the key intermediate [1(OCH3)]' could be successfully captured, and the detailed reaction mechanism has been explored with the aid of density functional theory (DFT) calculations, which were in excellent agreement with the experimental findings. All of the target complexes have been fully characterized by H-1, P-31{H-1}, and C-13{H-1} NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis.

Automated summary

A new class of complexes has been successfully synthesized and the reaction mechanism has been explored through experiments and DFT calculations. The substituents significantly affect the reaction rate, leading to the successful formation of the target complexes in the end.