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Spatial Separation of Molecular Conformers and Clusters

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

Thiaborane clusters with an exoskeletal B-H group.

Jan Vrána¹, Josef Holub, Maksim A Samsonov

¹Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Pardubice, Studentská 573, CZ-532 10, Czech Republic. ales.ruzicka@upce.cz.

Chemical Communications (Cambridge, England)

|March 1, 2019

Summary

New thiaborane compounds were synthesized by reacting closo-thiaboranes with N-bases. These compounds are unstable and hydrolyze to form ionic species, with some reactions leading to decaborane formation.

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Area of Science:

Inorganic Chemistry
Boron Chemistry
Heterocyclic Chemistry

Background:

Closocarboranes are cage-like boron hydride clusters with potential applications in materials science and medicine.
Understanding the reactivity of thiaboranes is crucial for developing new synthetic methodologies and exploring their unique properties.

Purpose of the Study:

To investigate the reactions of closo-1-SB11H11 and 12-I-closo-1-SB11H10 with N-bases.
To characterize the resulting thiaborane derivatives and their stability.
To explore the degradation pathways of these novel compounds.

Main Methods:

Reaction of closo-thiaboranes with 4-(dimethylamino)pyridine under inert conditions.
Characterization of products using spectroscopic techniques.
Investigation of compound stability in solution and air.
Analysis of hydrolysis products and reaction pathways with various N-bases.

Main Results:

Formation of nido-type thiaboranes with exoskeletal B-H groups stabilized by N-bases.
Demonstration of B-H moiety stabilization by bipyridine in a chelating manner.
Instability of the synthesized complexes in solution and air, leading to hydrolysis.
Generation of monodeboronated ionic compounds ([nido-7-SB10H11]- or [5-I-nido-7-SB10H10]- anions) as hydrolysis products.
Extrusion of boron and sulfur atoms upon reaction with 2,6-di-tert-butylpyridine, yielding decaborane.

Conclusions:

The reactions of closo-thiaboranes with N-bases yield diverse products, including novel nido-thiaboranes and ionic species.
The synthesized thiaborane complexes exhibit limited stability, undergoing hydrolysis and degradation.
The reactivity of thiaboranes can be tuned by the choice of N-base, leading to different reaction outcomes, including cage fragmentation.