A coordination chemistry dichotomy for icosahedral carborane-based ligands

Alexander M. Spokoyny, Charles W. MacHan, Daniel J. Clingerman, Mari S. Rosen, Michael J. Wiester, Robert D. Kennedy, Charlotte L. Stern, Amy A. Sarjeant, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

275 Scopus citations


Although the majority of ligands in modern chemistry take advantage of carbon-based substituent effects to tune the sterics and electronics of coordinating moieties, we describe here how icosahedral carboranes-boron-rich clusters-can influence metal-ligand interactions. Using a series of phosphine-thioether chelating ligands featuring meta- or ortho-carboranes grafted on the sulfur atom, we were able to tune the lability of the platinum-sulfur interaction of platinum(II)-thioether complexes. Experimental observations, supported by computational work, show that icosahedral carboranes can act either as strong electron-withdrawing ligands or electron-donating moieties (similar to aryl- or alkyl-based groups, respectively), depending on which atom of the carborane cage is attached to the thioether moiety. These and similar results with carborane-selenol derivatives suggest that, in contrast to carbon-based ligands, icosahedral carboranes exhibit a significant dichotomy in their coordination chemistry, and can be used as a versatile class of electronically tunable building blocks for various ligand platforms.

Original languageEnglish (US)
Pages (from-to)590-596
Number of pages7
JournalNature chemistry
Issue number8
StatePublished - Aug 2011

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering


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