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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.
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Stable Boron Dithiolene Radicals
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).
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- Award ID(s):
- 1661604
- PAR ID:
- 10061126
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 57
- Issue:
- 26
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 7865-7868
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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