Issue 5, 2016

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

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

Supplementary files

Article information

Article type
Research Article
Submitted
25 noy 2015
Accepted
22 fev 2016
First published
03 mar 2016

Inorg. Chem. Front., 2016,3, 711-717

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements