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A Stable Anionic Dithiolene Radical
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DOI：10.1021/jacs.7b03794.png)
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Abstract
En 中文
Sulfurization of anionic N-heterocyclic dicarbene, [:C{[N(2,6-(Pr2C6H3)-C-i)](2)CHCLi}(n) (2), with elemental sulfur (in a 1:2 ratio) in Et2O at low temperature gives 3 by inserting two sulfur atoms into the Li-C (i.e., C2 and C4) bonds in polymeric 2. Further reaction of 3 with 2 equiv of elemental sulfur in THF affords 4(center dot) via unexpected C-H bond activation, which represents the first anionic dithiolene radical to be structurally characterized in the solid state. Alternatively, 4(center dot) may also be synthesized directly by reaction of 1 with sulfur (in a 1:4 ratio) in THF. Reaction of 4(center dot) with GeCl2-dioxane gives an anionic germanium(W)-bis(dithiolene) complex (5). The nature of the bonding in 4(center dot) and 5 was probed by experimental and theoretical methods.
Keywords:
RAY-ABSORPTION SPECTROSCOPY
S BOND FORMATION
METAL-COMPLEXES
ELECTRONIC-STRUCTURE
NICKEL DITHIOLENES
NI
DERIVATIVES
ACTIVATION
REDUCTION
OXIDATION
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