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Issue 5, 2016
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Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions

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Abstract

We have developed a fast and efficient route to obtain perfunctionalized ether-linked alkyl and benzyl derivatives of the closo-[B12(OH)12]2− icosahedral dodecaborate cluster via microwave-assisted synthesis. These icosahedral boron clusters exhibit three-dimensional delocalization of the cage-bonding electrons, tunable photophysical properties, and a high degree of stability in air in both the solid state and in solution. A series of closo-[B12(OR)12]2−, hypocloso-[B12(OR)12]1− and hypercloso-[B12(OR)12]0 clusters have been prepared with reaction times ranging from hours to several minutes. This method is superior to previously reported protocols since it dramatically decreases the reaction times required and eliminates the need for inert atmosphere conditions. The generality of the new microwave-based method has been further demonstrated through the synthesis of several new derivatives, which feature redox potentials up to 0.6 V more positive than previously known B12(OR)12 cluster compounds. We further show how this method can be applied to a one-pot synthesis of hybrid, vertex-differentiated species B12(OR)11(OR′) that was formerly accessible only via multi-step reaction sequence.

Graphical abstract: Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions

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Supplementary files

Article information


Submitted
25 Nov 2015
Accepted
22 Feb 2016
First published
03 Mar 2016

Inorg. Chem. Front., 2016,3, 711-717
Article type
Research Article
Author version available

Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions

A. I. Wixtrom, Y. Shao, D. Jung, C. W. Machan, S. N. Kevork, E. A. Qian, J. C. Axtell, S. I. Khan, C. P. Kubiak and A. M. Spokoyny, Inorg. Chem. Front., 2016, 3, 711
DOI: 10.1039/C5QI00263J

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