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. 2021 Dec 20;60(24):19165-19174.
doi: 10.1021/acs.inorgchem.1c02981. Epub 2021 Dec 2.

Icosahedral m-Carboranes Containing Exopolyhedral B-Se and B-Te Bonds

Harrison A Mills  1 , Fadi Alsarhan  1 , Ta-Chung Ong  1 , Milan Gembicky  2 , Arnold L Rheingold  2 , Alexander M Spokoyny  1   3
Affiliations

Icosahedral m-Carboranes Containing Exopolyhedral B-Se and B-Te Bonds

Harrison A Mills et al. Inorg Chem. .

Abstract

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.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Figure 1:
Figure 1:
A. Literature examples of tricoordinate boron centers containing a boron-chalcogen single bond or double bond. B. Literature examples of tetracoordinate boron centers containing boron-chalcogen single bonds. C. Extent of previous studies regarding the reactivity of B-Se and B-Te containing carboranes. Nucleophilic reactivity has been shown between carboranyl chalcogenolates (Y = Se, Te) and electrophilic reactivity has been shown with carboranyl selenyl (II) chlorides, though not with tellurenyl (II) or (IV) chlorides.
Figure 2:
Figure 2:
This work, overview of compounds synthesized by the electrophilic and nucleophilic reactions of selenium and tellurium-containing meta-carboranes.
Figure 3:
Figure 3:
A. Synthesis of dichalcogenides 1A and 1B including their respective crystallographically derived structures. Thermal ellipsoids are drawn at 50% probability, hydrogens are omitted for clarity. B. Synthesis of electrophilic selenyl (II), tellurenyl (II), and tellurenyl (IV) reagents 2A, 3A, and 4A from carboranyl dichalcogenides. Comparison of 11B and 125Te NMR for compounds 1B, 3A, and 4A.
Figure 4:
Figure 4:
Reactions of 2A with common carbon-based nucleophiles. aReaction was performed in anhydrous diethyl ether under an inert atmosphere at r.t.. bReaction was performed in anhydrous dichloromethane at r.t.. cReaction was performed in anhydrous toluene with 2 eq. of AlCl3 at 50 °C. See SI for full experimental details. Thermal ellipsoids are drawn at 50% probability, hydrogens are omitted for clarity.
Figure 5:
Figure 5:
A. Reaction of 3A with phenylmagnesium bromide in anhydrous Et2O and phenylacetylene in various solvents. B. Reaction of 4A with phenylacetylene, including in situ 11B and 125Te NMR characterization of reaction intermediates, 4B* and 4B*’.
Figure 6:
Figure 6:
A. SNAr of 5A and 6A with perfluorotoluene. 77Se and 125Te NMR of 5B and 6B. B. Reaction of 6A with palladium oxidative addition complex.
See this image and copyright information in PMC

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