Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 21, Issue 11, Pages 5903-5915Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8cp05313h
Keywords
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Funding
- Feodor Lynen Fellowship of the Alexander von Humboldt Foundation
- Deutsche Forschungsgemeinschaft (DFG) [FI 1628/2-2]
- BES Separations and Analysis Program at PNNL
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences at Pacific Northwest National Laboratory
- Office of Biological and Environmental Research
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
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closo-Borate anions [closo-BnXn](2-) re part of the most famous textbook examples of polyhedral compounds. Substantial differences in their reactivity and interactions with other compounds depending on the substituent X and cluster size n have been recognized, which favor specific closo-borates for different applications in cancer treatment, chemical synthesis, and materials science. Surprisingly, a fundamental understanding of the molecular properties underlying these differences is lacking. Here, we report our study comparing the electronic structure and reactivity of closo-borate anions [closo-BnXn](2-) (X = Cl, Br, I, n = 10, 11, 12 in all combinations) in the gas phase and in solution. We investigated the free dianions and the ion pairs [nBu(4)N](+)[closo-BnXn](2-) by gas phase anion photoelectron spectroscopy accompanied by theoretical investigations. Strong similarities in electronic structures for n = 10 and 11 were observed, while n = 12 clusters were different. A systematic picture of the development in electronic stability along the dimension X is derived. Collision induced dissociation shows that fragmentation of the free dianions is mainly dependent on the substituent X and gives access to a large variety of boron-rich molecular ions. Fragmentation of the ion pair depends strongly on n. The results reflect the high chemical stability of clusters with n = 10 and 12, while those with n = 11 are much more prone to dissociation. We bridge our study to the condensed phase by performing comparative electrochemistry and reactivity studies on closo-borates in solution. The trends found at the molecular level are also reflected in the condensed-phase properties. We discuss how the gas phase values allow evaluation of the influence of the condensed phase on the electronic stability of closo-borates. A synthetic method via an oxidation/chlorination reaction yielding [closo-B10Cl10](2-) from highly chlorinated {closo-B-11} clusters is introduced, which underlines the intrinsically high reactivity of the {closo-B-11} cage.
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