By the same authors

From the same journal

From the same journal

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

Research output: Contribution to journalArticle

Full text download(s)

  • AAM

    1 MB, PDF document

Published copy (DOI)

Author(s)

Department/unit(s)

Publication details

JournalInorganic Chemistry
DateAccepted/In press - 12 Dec 2016
DateE-pub ahead of print - 22 Dec 2016
DatePublished (current) - 17 Jan 2017
Issue number2
Volume56
Number of pages9
Pages (from-to)852-860
Early online date22/12/16
Original languageEnglish

Abstract

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.

Bibliographical note

© 2016 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

Discover related content

Find related publications, people, projects, datasets and more using interactive charts.

View graph of relations