B−B bond nucleophilicity in a tetraaryl μ‐hydridodiborane(4) anion

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 li
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].
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Metadaten
Author:Timo Trageser, Michael Bolte, Hans‐Wolfram Lerner, Matthias Wagner
URN:urn:nbn:de:hebis:30:3-564987
DOI:http://dx.doi.org/10.1002/anie.202000292
ISSN:1521-3773
ISSN:1433-7851
Parent Title (German):Angewandte Chemie. International edition
Publisher:Wiley-VCH
Place of publication:Weinheim
Document Type:Article
Language:English
Date of Publication (online):2020/02/14
Date of first Publication:2020/02/14
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2020/12/09
Volume:59
Issue:20
Pagenumber:6
First Page:7726
Last Page:7731
HeBIS PPN:476111412
Institutes:Biochemie und Chemie
Dewey Decimal Classification:540 Chemie und zugeordnete Wissenschaften
Sammlungen:Universitätspublikationen
Licence (German):License LogoCreative Commons - Namensnennung-Nicht kommerziell - Keine Bearbeitung 4.0

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