TY  - JOUR
A1  - Trageser, Timo
A1  - Bolte, Michael
A1  - Lerner, Hans-Wolfram
A1  - Wagner, Matthias
T1  - B−B bond nucleophilicity in a tetraaryl μ‐hydridodiborane(4) anion
T2  - Angewandte Chemie. International edition
N2  - The tetraaryl μ‐hydridodiborane(4) anion [2H]− possesses nucleophilic B−B and B−H bonds. Treatment of K[2H] with the electrophilic 9‐H‐9‐borafluorene (HBFlu) furnishes the B3 cluster K[3], with a triangular boron core linked through two BHB two‐electron, three‐center bonds and one electron‐precise B−B bond, reminiscent of the prominent [B3H8]− anion. Upon heating or prolonged stirring at room temperature, K[3] rearranges to a slightly more stable isomer K[3 a]. The reaction of M[2H] (M+=Li+, K+) with MeI or Me3SiCl leads to equimolar amounts of 9‐R‐9‐borafluorene and HBFlu (R=Me or Me3Si). Thus, [2H]− behaves as a masked [:BFlu]− nucleophile. The HBFlu by‐product was used in situ to establish a tandem substitution‐hydroboration reaction: a 1:1 mixture of M[2H] and allyl bromide gave the 1,3‐propylene‐linked ditopic 9‐borafluorene 5 as sole product. M[2H] also participates in unprecedented [4+1] cycloadditions with dienes to furnish dialkyl diaryl spiroborates, M[R2BFlu].
Y1  - 2020
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/56498
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-564987
SN  - 1521-3773
SN  - 1433-7851
VL  - 59
IS  - 20
SP  - 7726
EP  - 7731
PB  - Wiley-VCH
CY  - Weinheim
ER  -