Reaction of carbene‐stabilized disilicon (
Carbene-mediated synthesis of a germanium tris(dithiolene)dianion
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.
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- Award ID(s):
- 1855641
- 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. -
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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 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. -
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
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Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0cc08206f
