The Synthesis of 10-Halo-Substituted Derivatives of nido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]- and New Linear Correlations Between NMR Parameters

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Title:The Synthesis of 10-Halo-Substituted Derivatives of nido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]- and New Linear Correlations Between NMR Parameters
Creators:
Holub, Josef
Bakardjiev, Mario
Štíbr, Bohumil
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 70, 11, pp. 1861-1872
Uncontrolled Keywords:Halogenations, Phosphacarboranes, Heterodicarbaboranes, Phosphadicarbaboranes, Borane clusters, Boron, Carboranes, NMR spectroscopy

Abstract

Halogenation of the eleven-vertex phosphadicarbaborane <i>nido</i>-7,8,9-PC<sub>2</sub>B<sub>8</sub>H<sub>10</sub> (<strong>1</strong>) with CCl<sub>4</sub>, Br<sub>2</sub> or I<sub>2</sub> in the presence of anhydrous AlCl<sub>3</sub> (solvents CCl<sub>4</sub>, CS<sub>2</sub>, and benzene, respectively) generated a series of 10-X-<i>nido</i>-7,8,9-PC<sub>2</sub>B<sub>8</sub>H<sub>10</sub> (10-X-<strong>1</strong>) compounds (X = Cl, Br, and I) in yields 55, 65, and 63%, respectively. Anionic compounds [10-X-<i>nido</i>-7,8,9-PC<sub>2</sub>B<sub>8</sub>H<sub>10</sub>]<sup>-</sup> (10-X-<strong>2</strong>) (X = Cl, Br, I) were obtained by treatment of the corresponding neutral compounds with "proton sponge" (PS = 1,8-bis(dimethylamino)naphthalene). All compounds were characterized by multinuclear (<sup>11</sup>B, <sup>1</sup>H, and <sup>31</sup>P) NMR spectroscopy and [<sup>11</sup>B-<sup>11</sup>B]-COSY and <sup>1</sup>H-{<sup>11</sup>B(selective)} NMR measurements that led to complete assignments of all <sup>11</sup>B and <sup>1</sup>H resonances to individual cluster positions. Interesting halo-substitution NMR effects are also discussed in terms of new linear correlations. All the changes in NMR chemical shifts (∆) induced at the various skeletal sites by halogeno substituents on specific sites can be related to an arbitrary reference skeleton and are, within experimental errors, linearly proportional to those induced at the substituted site (∆α) of the reference skeleton. <p>

Title:The Synthesis of 10-Halo-Substituted Derivatives of nido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]- and New Linear Correlations Between NMR Parameters
Creators:
Holub, Josef
Bakardjiev, Mario
Štíbr, Bohumil
Uncontrolled Keywords:Halogenations, Phosphacarboranes, Heterodicarbaboranes, Phosphadicarbaboranes, Borane clusters, Boron, Carboranes, 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:70
Number:11
Page Range:pp. 1861-1872
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20051861UNSPECIFIED
ID Code:2444
Item Type:Article
Deposited On:06 Feb 2009 17:18
Last Modified:06 Feb 2009 16:18

Citation

Holub, Josef; Bakardjiev, Mario; Štíbr, Bohumil (2005) The Synthesis of 10-Halo-Substituted Derivatives of nido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]- and New Linear Correlations Between NMR Parameters. Collection of Czechoslovak Chemical Communications, 70 (11). pp. 1861-1872. ISSN 0010-0765

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