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Iridium‐Induced Regioselective B−H and C−C Activations at Azo‐Substituted o ‐Carboranes
Author(s) -
Gao Yang,
Cui PengFei,
Aznarez Francisco,
Jin GuoXin
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801381
Subject(s) - regioselectivity , iridium , chemistry , rhodium , carborane , reactivity (psychology) , medicinal chemistry , stereochemistry , solvent , catalysis , organic chemistry , medicine , alternative medicine , pathology
p ‐Methoxybenzeneazo‐substituted o ‐carboranes have been synthesized and their reactivity with half‐sandwich iridium and rhodium complexes has been investigated in detail. A variety of solvent‐ and base‐dependent, highly site‐selective B−H and C−C σ‐bond activations at the C/B cage have been observed. While the use of CH 3 OH leads to the formation of metallacarboranes, o ‐carborane clusters undergo cyclometallation reactions involving B(6)−H, B(4)−H or a rare B(7)−H activation in CH 2 Cl 2 . The synthesis of a unique pseudo‐ closo ‐iridacarborane through a very unconventional metal‐mediated C cage −C cage activation is described in this contribution.