A coordination chemistry dichotomy for icosahedral carborane-based ligands

作者：Spokoyny Alexander M^*; Machan Charles W; Clingerman Daniel J; Rosen Mari S; Wiester Michael J; Kennedy Robert D; Stern Charlotte L; Sarjeant Amy A; Mirkin Chad A

来源：Nature Chemistry, 2011, 3(8): 590-596.

DOI：10.1038/NCHEM.1088

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.

• 出版日期2011-8
• 单位西北大学