Reaction of carbene‐stabilized disilicon (
- Award ID(s):
- 1855641
- NSF-PAR ID:
- 10318336
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 57
- Issue:
- 20
- ISSN:
- 1359-7345
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract 1 ) with the lithium‐based dithiolene radical (2. ) affords the first dianionic silicon tris(dithiolene) complex (3 ). Notably, the formation of3 represents the unprecedented utilization of carbene‐stabilized disilicon (1 ) as a silicon‐transfer agent. The nature of3 was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations. -
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 of3 represents the unprecedented utilization of carbene‐stabilized disilicon (1 ) as a silicon‐transfer agent. The nature of3 was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations. -
Abstract Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical
1 .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). -
Abstract Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical
1 .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). -
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