More Like this

1. 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. 

   more » « less
2. Carbene-mediated synthesis of a germanium tris(dithiolene)dianion

   https://doi.org/10.1039/d0cc08206f  

   Tran, Phuong M.; Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; Schaefer, Henry F.; Robinson, Gregory H. (March 2021, Chemical Communications)

   While the 1 : 1 reaction of 3 with an N-heterocyclic carbene ({(Me)CN(i-Pr)} 2 C:) in THF resulted in ligand-substituted product 4, the corresponding 1 : 2 reaction (in the presence of H 2 O) gives the first structurally characterized germanium tris(dithiolene)dianion 5 as the major product and the “naked” dithiolene radical 6˙ as a minor by-product. The structure and bonding of 4 and 5 were probed by experimental and theoretical methods. Our study suggests that carbene-mediated partial hydrolysis may represent a new method to access tris(dithiolene) complexes of main-group elements. 

   more » « less
3. 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)

   Abstract 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). 

   more » « less
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)

   Abstract 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. 

   more » « less
5. Carbene‐Stabilized Disilicon as a Silicon‐Transfer Agent: Synthesis of a Dianionic Silicon Tris(dithiolene) Complex

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

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

   Abstract 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. 

   more » « less