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. 2020 Oct 14;142(41):17301-17305.
doi: 10.1021/jacs.0c08495. Epub 2020 Oct 2.

A Stable Naked Dithiolene Radical Anion and Synergic THF Ring-Opening

Yuzhong Wang  1 , Yaoming Xie  1 , Pingrong Wei  1 , Soshawn A Blair  1 , Dongtao Cui  1 , Michael K Johnson  1 , Henry F Schaefer 3rd  1 , Gregory H Robinson  1
Affiliations

A Stable Naked Dithiolene Radical Anion and Synergic THF Ring-Opening

Yuzhong Wang et al. J Am Chem Soc. .

Abstract

Reaction of the lithium dithiolene radical 2• with the imidazolium salt [{(Me)CN(i-Pr)}2CH]+[Cl]- (in a 1:1 molar ratio) gives the first stable naked anionic dithiolene radical 3•, which, when coupled with hexasulfide, [{(Me)CN(i-Pr)}2CH]+2[S6]2- (4), and N-heterocyclic silylene 5, unexpectedly results in synergic THF ring-opening via a radical mechanism.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
(a) Room-temperature X-band EPR spectrum of 3• in THF, recorded at 9.584 GHz with a modulation amplitude of 0.02 mT and a microwave power of 1 mW. (b) SOMO of [3•]−.
Figure 2.
Figure 2.
Molecular structure of 3•. Thermal ellipsoids represent 30% probability. Hydrogen atoms have been omitted for clarity. Selected bond distances (Å) and angles (deg): S(1)−C(1), 1.6591(18); C(2)−C(3), 1.420(2); C(2)−S(2), 1.6637(18); C(3)−S(3), 1.6698(18); C(2)−C(3)−S(3), 129.87(14). Nonbonding distances (Å): S(2)···H(28), 3.004; S(3)···H(28), 2.902.
Figure 3.
Figure 3.
Molecular structures of [6]2− and [7]2−. Thermal ellipsoids represent 30% probability. Hydrogen atoms have been omitted for clarity. Selected bond distances (Å) and angles (deg): For [6]2−, S(1)−C(1), 1.677(3); C(2)−C(3), 1.356(3); C(2)−S(2), 1.726(2); C(3)−S(3), 1.710(3); Si(1)−O(1), 1.6534(19); Si(1)−S(4), 2.0135(10); C(2)−C(3)−S(3), 131.6(2); C(3)−C(2)−S(2), 128.7(2); O(1)−Si(1)−S(4), 112.01(8); N(3)−Si(1)−N(4), 90.20(10). For [7]2−, S(1)−C(1), 1.661(6); C(2)−C(2A), 1.347(7); C(2)−S(2), 1.734(4); Si(1)−O(1), 1.640(3); Si(1)−S(3), 2.0206(15); C(2A)−C(2)−S(2), 128.82(14); O(1)−Si(1)−S(3), 110.74(12); N(2)−Si(1)−N(3), 90.14(15).
Scheme 1.
Scheme 1.
Synthesis of Naked Anionic Dithiolene Radical 3• (R = 2,6-Diisopropylphenyl)
Scheme 2.
Scheme 2.
Synergic THF Ring-Opening by 3• and NHSiDipp (5) in the Presence of the Hexasulfide (4) (R = 2,6-Diisopropylphenyl)
Scheme 3.
Scheme 3.
Proposed Mechanism of the Synthesis of 6 and 7a aThe cation moieties of 3•, 4, 6, and 7 have been omitted for clarity.
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