The Oxidative Cycloaddition of Metal Dithiolenes to Olefins. Synthesis and Characterization of Norbornadiene—Bis-cis-(1,2-pernuoromethylethene-1,2-dithiolato) nickel

Abstract

Reaction of Ni[S2C2(CF3)2]2 with norbornadiene and norbornene gives products which appear to be formed by the oxidative addition of the inorganic complex to the olefin. The structure of the norbornadiene adduct has been established by a single-crystal X-ray diffraction study. Briefly, the structure shows that two sulfur-carbon bonds have been formed between the reactants and that one of the norbornadiene carbon-carbon double bonds has been transformed into a single bond. The sulfur atoms are in the exo configuration, with one from each ligand being involved in the new bonds, which are about 0.1 Å longer than the sulfur-carbon bonds within the ligands. The structural, spectroscopic, and electrochemical properties of the adducts closely resemble those of the dianionic form of the nickel complex, suggesting that the reaction be considered an oxidative cycloaddition. The crystals studied were triclinic, P1, with a0 = 11.76 Å, b0 = 12.85 Å, C0 = 8.15 Å, α = 105.8°, β = 78.7°, and γ = 122.0°, with the unit cell containing two formula units. The structure was solved using 1606 visually estimated unique reflections collected by a film method and refined to a final R factor of 10.7% based on F. © 1970, American Chemical Society. All rights reserved.