The reaction of Pt(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] with excess 2,3-dimethyl-1,3-butadiene initially yields the expected 1:1 adduct, in which the diene has added across two sulfur atoms on separate tfd ligands. However, within 1 day at 50 degrees C, this kinetic product quantitatively converts into a thermodynamic product where two dienes have added to one tfd ligand via unprecedented addition across the dithiolene CS bonds. The new reaction is highly selective for the C(2)-symmetric diastereomer. A new chiral bisthioether chelate ligand has formed in the product, which has been characterized crystallographically.
A bis-double-decker complex has been assembled from the nickel bisdithiolene complex [Ni(S 2C 2Me 2) 2] (1-/2-) and two [Cp*Fe] (+) units (Cp* = C 5Me 5). The complex, [(eta (5)-Cp*-Fe-mu-eta (5),eta (5)-((S 2C 2Me 2) 2Ni)Fe-eta (5)-Cp*] ( n ) ( 1 ( n )), was isolated in two charge states ( n = 0, 1). The structure of 1 (+) was confirmed by X-ray crystallography for 1 (+)PF 6 (-) and 1 (+)BF 4 (-), and it shows the nickel bisdithiolene units pi-donating to iron centers. Both salts crystallize in a centrosymmetric space group (center of inversion at nickel). Computational (density functional theory) data indicate a highly delocalized spin density for 1 (+). The reaction of 1 with 1 or 2 equiv of HBF 4 leads to oxidation to form 1 (+) or 1 (2+), respectively. On an electrochemical time scale, reversibility is observed for the redox series 1/ 1 (+)/ 1 (2+), with an additional slower step for oxidation of 1 (2+).
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