Open AccessIcosahedral m-Carboranes Containing Exopolyhedral B–Se and B–Te Bonds
Author(s) -
Harrison A. Mills,
Fadi Alsarhan,
TaChung Ong,
Milan Gembický,
Arnold L. Rheingold,
Alexander M. Spokoyny
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c02981
Subject(s) - chemistry , nucleophile , electrophile , chalcogen , reactivity (psychology) , substitution reaction , electrophilic aromatic substitution , reagent , nucleophilic substitution , medicinal chemistry , electrophilic addition , molecule , stereochemistry , crystallography , organic chemistry , catalysis , medicine , alternative medicine , pathology
Chalcogen-containing carboranes have been known for several decades and possess stable exopolyhedral B(9)-Se and B(9)-Te σ bonds despite the electron-donating ability of the B(9) vertex. While these molecules are known, little has been done to thoroughly evaluate their electrophilic and nucleophilic behavior. Herein, we report an assessment of the electrophilic reactivity of m -carboranylselenyl(II), -tellurenyl(II), and -tellurenyl(IV) chlorides and establish their reactivity pattern with Grignard reagents, alkenes, alkynes, enolates, and electron-rich arenes. These electrophilic reactions afford unique electron-rich B-Y-C (Y = Se, Te) bonding motifs not commonly found before. Furthermore, we show that m -carboranylselenolate, and even m -carboranyltellurolate, can be competent nucleophiles and participate in nucleophilic aromatic substitution reactions. Arene substitution chemistry is shown to be further extended to electron-rich species via palladium-mediated cross-coupling chemistry.