Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical
Stable Boron Dithiolene Radicals
Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical
- 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
More Like this
-
more » « less
Abstract 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). -
more » « less
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. -
more » « less
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. -
more » « less
Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (
2 ) with GeCl2 • dioxane in THF/TMEDA gives3 , a TMEDA‐complexed dithiolene‐based germylene. Compound3 is 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 , and8 was investigated by both experimental and theoretical methods. -
more » « less
Abstract The previously unknown silylgermylidyne radical (H3SiGe; X2A′′) was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X2Π) with germane (GeH4; X1A1) under single collision conditions in crossed molecular beams experiments. This reaction begins with the formation of a van der Waals complex followed by insertion of silylidyne into a germanium‐hydrogen bond forming the germylsilyl radical (H3GeSiH2). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H2GeSiH3), which undergoes a hydrogen shift to an exotic, hydrogen‐bridged germylidynesilane intermediate (H3Si(μ‐H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H3SiGe). Our study offers a remarkable glance at the complex reaction dynamics and inherent isomerization processes of the silicon‐germanium system, which are quite distinct from those of the isovalent hydrocarbon system (ethyl radical; C2H5) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon‐germanium species at the microscopic level exploiting crossed molecular beams.
