- PAR ID:
- 10118807
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 55
- Issue:
- 56
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 8087 to 8089
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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
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Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (
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Abstract Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical
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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). -
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