Geminal dithiols

Unprecedented Formation of the First Alkaline‐Earth‐Metal Complex Bearing an Asymmetrical gem‐Dithiolato Heteroscorpionato Ligand

“…Quite unexpectedly, the reaction with C 3 H 5 MgCl led to the complex [Mg(κ 3 -NNS-μ-S-bppbte)] 3 (1) [bppbte = 1,1-bis(3,5-dimethyl-1H-pyrazol-1-yl)pent-4-ene-2,2-bis(thiolate)], which bears an asymmetrical gem-dithiolato heteroscorpionato ligand in a κ 3 -NNS-μ-S coordination mode. The complex was isolated in quantitative yield (ca.…”

“…This process is particularly noteworthy, because it led to the formation of the first gem-dithiolate-containing alkaline-earth-metal species through a procedure that has no precedent in the literature. [1] Scheme 1. Reactions for the preparation of the gem-dithiolato (1) and the sandwich (2) heteroscorpionato magnesium complexes.…”

“…To the best of our knowledge, examples of the formation of asymmetrical gem-dithiolates through an insertion reaction of a Grignard reagent into a dithioacetate fragment have not been reported previously. [1] Results and Discussion Synthesis and Characterization of the gem-Dithiolato (1) and the Sandwich (2) Heteroscorpionato Magnesium Complexes…”

“…In this situation, the magnesium atom is surrounded in an octahedral manner, and there is a plane of symmetry, which contains both the dithioacetato groups and the magnesium metal center (Scheme 1, b). Additionally, 1 H NOESY-1D experiments were performed to confirm the assignment of the signals for the Me 3 and Me 5 groups, and 1 H-13 C heteronuclear correlation (g-HSQC) experiments were also carried out to assign the resonances for C 4 , Me 3 , and Me 5 . Complex 1 was unambiguously characterized by X-ray diffraction studies of single crystals, which were easily grown from a toluene solution at -26°C.…”

“…A few examples have been successfully synthesized and structurally characterized, and these mainly contain late transition metals. [1] The vast majority of this class of complexes contain symmetrically substituted gem-dithiolates [(μ-S 2 CR 2 )…”