Revisiting B20H16 by means of a joint computational/experimental NMR approach

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Title:Revisiting B20H16 by means of a joint computational/experimental NMR approach
Creators:
Hnyk, Drahomír
Holub, Josef
Jelínek, Tomáš
Macháček, Jan
Londesborough, Michael G. S.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 75, 11, pp. 1115-1123
Uncontrolled Keywords:Clusters, <i>Ab initio</i> calculations, Boron, NMR spectroscopy

Abstract

A new synthesis of the fused macropolyhedral boron cluster B<sub>20</sub>H<sub>16</sub> is described and its molecular structure in solution discussed, based on multi-nuclear NMR spectra, including <i>COSY</i> measurements, in relation to its previously elucidated solid-state structure. To verify the conclusions from the NMR study, experimentally determined chemical shifts are compared with calculated values at the GIAO-B3LYP level with a TZP basis set by Huzinaga. There is a very good agreement between the experimental and computed δ(<sup>11</sup>B) values, suggesting that the MP2/6-31G* internal coordinates are a reasonable representation of the molecular geometry of this twenty-vertex cluster in solution that is essentially the same as its solid-state structure. A computational analysis of the FMO orbitals of B<sub>20</sub>H<sub>16</sub>, in particular of the LUMO, reveals that the four naked boron atoms, common for two shared icosahedral subclusters, are the reactive sites of this <i>D</i><sub>2d</sub>-symmetrical molecule.

Title:Revisiting B20H16 by means of a joint computational/experimental NMR approach
Creators:
Hnyk, Drahomír
Holub, Josef
Jelínek, Tomáš
Macháček, Jan
Londesborough, Michael G. S.
Uncontrolled Keywords:Clusters, <i>Ab initio</i> calculations, Boron, NMR spectroscopy
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:75
Number:11
Page Range:pp. 1115-1123
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc2010073UNSPECIFIED
ID Code:6266
Item Type:Article
Deposited On:12 Nov 2010 12:04
Last Modified:12 Nov 2010 11:04

Citation

Hnyk, Drahomír; Holub, Josef; Jelínek, Tomáš; Macháček, Jan; Londesborough, Michael G. S. (2010) Revisiting B20H16 by means of a joint computational/experimental NMR approach. Collection of Czechoslovak Chemical Communications, 75 (11). pp. 1115-1123.

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