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1. Carbene‐Stabilized Disilicon as a Silicon‐Transfer Agent: Synthesis of a Dianionic Silicon Tris(dithiolene) Complex

   https://doi.org/10.1002/anie.201916395  

   Wang, Yuzhong ; Tope, Cynthia A. ; Xie, Yaoming ; Wei, Pingrong ; Urbauer, Jeffrey L. ; Schaefer, III, Henry F. ; Robinson, Gregory H. ( April 2020 , Angewandte Chemie International Edition)

   Reaction of carbene‐stabilized disilicon (1) with the lithium‐based dithiolene radical (2^.) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of3represents the unprecedented utilization of carbene‐stabilized disilicon (1) as a silicon‐transfer agent. The nature of3was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations.

    

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2. Stable Boron Dithiolene Radicals

   https://doi.org/10.1002/anie.201804298  

   Wang, Yuzhong ; Xie, Yaoming ; Wei, Pingrong ; Blair, Soshawn A. ; Cui, Dongtao ; Johnson, Michael K. ; Schaefer, III, Henry F. ; Robinson, Gregory H. ( May 2018 , Angewandte Chemie International Edition)

   Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical1^.with boron bromide gives the dibromoboron dithiolene radical2^., the parallel reaction of1^.with (C₆H₁₁)₂BCl (0 °C) affords the dicyclohexylboron dithiolene radical3^.. Radicals2^.and3^.were characterized by single‐crystal X‐ray diffraction, UV/Vis, and EPR spectroscopy. The nature of these radicals was also probed computationally. Under mild conditions,3^.undergoes unexpected thiourea‐mediated B−C bond activation to give zwitterion4, which may be regarded as an anionic dithiolene‐modified carbene complex of the sulfenyl cation RS⁺(R=cyclohexyl).

    

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3. Stable Boron Dithiolene Radicals

   https://doi.org/10.1002/ange.201804298  

   Wang, Yuzhong ; Xie, Yaoming ; Wei, Pingrong ; Blair, Soshawn A. ; Cui, Dongtao ; Johnson, Michael K. ; Schaefer, III, Henry F. ; Robinson, Gregory H. ( May 2018 , Angewandte Chemie)

   Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical1^.with boron bromide gives the dibromoboron dithiolene radical2^., the parallel reaction of1^.with (C₆H₁₁)₂BCl (0 °C) affords the dicyclohexylboron dithiolene radical3^.. Radicals2^.and3^.were characterized by single‐crystal X‐ray diffraction, UV/Vis, and EPR spectroscopy. The nature of these radicals was also probed computationally. Under mild conditions,3^.undergoes unexpected thiourea‐mediated B−C bond activation to give zwitterion4, which may be regarded as an anionic dithiolene‐modified carbene complex of the sulfenyl cation RS⁺(R=cyclohexyl).

    

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4. Germanium(II) Dithiolene Complexes

   https://doi.org/10.1002/chem.202302258  

   Tran, Phuong M. ; Wang, Yuzhong ; Lahm, Mitchell E. ; Wei, Pingrong ; Molnar, Christopher J. ; Schaefer, III, Henry F. ; Robinson, Gregory H. ( October 2023 , Chemistry – A European Journal)

   The 1 : 2 reaction of the imidazole‐based dithiolate (2) with GeCl₂ • dioxane in THF/TMEDA gives3, a TMEDA‐complexed dithiolene‐based germylene. Compound3is converted to monothiolate‐complexed (5) and N‐heterocyclic carbene‐complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis‐dithiolene‐based germylene (8), involving a 3c–4e S‐Ge‐S bond, has also been synthesized through controlled hydrolysis of7. The bonding nature of3,5, and8was investigated by both experimental and theoretical methods.

    

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5. Lewis base-complexed magnesium dithiolenes

   https://doi.org/10.1039/C9CC03427G  

   Wang, Yuzhong ; Maxi, Nirva A. ; Xie, Yaoming ; Wei, Pingrong ; Schaefer, Henry F. ; Robinson, Gregory H. ( July 2019 , Chemical Communications)

   The first magnesium-based dithiolene, 2 , was prepared by reaction of the lithium dithiolene radical, 1˙ , with 2-mesitylmagnesium bromide. Reaction of 2 with N-heterocyclic carbenes (in toluene) gave a carbene-stabilized magnesium monodithiolene complex, 3 . Complex 3 , in turn, is readily converted to a THF-solvated magnesium bis-dithiolene dianion, 4 , via partial hydrolysis in polar solvents ( i.e. , THF/CH 3 CN). Compounds 2 , 3 and 4 have been spectroscopically and structurally characterized and probed by DFT computations. 

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