In:
Angewandte Chemie International Edition, Wiley, Vol. 61, No. 15 ( 2022-04-04)
Abstract:
Although Schleyer's computations in 1979 predicted that the ground state of the parent diborirane features a planar‐tetracoordinate carbon atom (anti van't Hoff–Le Bel geometry), this work demonstrates that substitution of C coupled with N‐heterocyclic carbene (NHC) coordination provides access to isolable diborirane derivatives 3 and 4 with van't Hoff–Le Bel geometry. Species 3 and 4 are isoelectronic with cyclopropane and the highly strained B 2 C rings feature 2c–2e bent σ bonds. Consequently, the B−B and B−C bonds in 3 are cleaved in the presence of hydride, proton, and chalcogens. The former two reactions gave NHC‐coordinated fluorenyldihydridoborane 5 and dichlorofluorenylborane 6 , respectively, whereas the latter transformations afforded novel thiaborirane 8 and selenaborirane 9 . In addition, transfer hydrogenation of 3 with ammonia borane (H 3 N⋅BH 3 ) led to the formation of (μ‐hydrido)diborane 7 via selective cleavage of the B−B bond. These reactivities show potential for their future application in organic synthesis.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202117053
Language:
English
Publisher:
Wiley
Publication Date:
2022
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7
