Unusual cage rearrangements in 10-vertex nido-5,6-dicarbaborane derivatives: An interplay between theory and experiment

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F17%3A00470382" target="_blank" >RIV/61388980:_____/17:00470382 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b02320" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.6b02320</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b02320" target="_blank" >10.1021/acs.inorgchem.6b02320</a>

Result language
angličtina
Original language name
Unusual cage rearrangements in 10-vertex nido-5,6-dicarbaborane derivatives: An interplay between theory and experiment
Original language description
The reaction between selected X-nido-5,6-C2B8H11 compounds (where X = Cl, Br, I) and "Proton Sponge" [PS 1,8-bis(dimethylamino)naphthalene], followed by acidification, results in extensive rearrangement of all cage vertices. Specifically, deprotonation of 7-X-5,6-C2B8H11 compounds with one equivalent of PS in hexane or CH2Cl2 at ambient temperature led to a 7 → 10 halogen rearrangement, forming a series of PSH+[10-X-5,6-C2B8H10]- salts. Reprotonation using concentrated H2SO4 in CH2Cl2 generates a series of neutral carbaboranes 10-X-5,6-C2B8H11, with the overall 7 → 10 conversion being 75%, 95%, and 100% for X = Cl, Br, and I, respectively. Under similar conditions, 4-Cl-5,6-C2B8H11 gave ∼66% conversion to 3- Cl-5,6-C2B8H11. Since these rearrangements could not be rationalized using the Bvertex swing mechanism, new cage rearrangement mechanisms, which are substantiated using DFT calculations, have been proposed. Experimental 11B NMR chemical shifts are well reproduced by the computations as expected δ(11B) for B(10) atoms in derivatives with X = Br and I are heavily affected by spin-orbit coupling.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry

Project
<a href="/en/project/GA16-01618S" target="_blank" >GA16-01618S: Ten-vertex dicarbaborane molecular assemblies via alkylation</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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