Polyhedral Monocarbaborane Chemistry. Functionality and Isomerism: Reactions of the [6-Ph-nido-6-CB9H11]- Anion with Aminopyridines NC5H4NH2 to Yield Neutral arachno and closo Ten-Vertex Monocarbaborane Derivatives

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Title:Polyhedral Monocarbaborane Chemistry. Functionality and Isomerism: Reactions of the [6-Ph-nido-6-CB9H11]- Anion with Aminopyridines NC5H4NH2 to Yield Neutral arachno and closo Ten-Vertex Monocarbaborane Derivatives
Creators:
Bullen, Neil J.
Kennedy, John D.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 70, 11, pp. 1873-1890
Uncontrolled Keywords:Dihydrogen bonding, Crystal and molecular structure, X-Ray diffraction, Monocarbaboranes, Boranes, Pyridine adducts, Amine-functionalised carbaboranes, Carboranes, NMR spectroscopy

Abstract

Reaction of NC<sub>5</sub>H<sub>4</sub>-2-NH<sub>2</sub> with the [6-Ph-<i>nido</i>-6-CB<sub>9</sub>H<sub>11</sub>]<sup>-</sup> anion (<strong>1</strong>) in the presence of hydrated FeCl<sub>3</sub> gives [6-Ph-9-(NC<sub>5</sub>H<sub>4</sub>-2-NH<sub>2</sub>)-<i>arachno</i>-6-CB<sub>9</sub>H<sub>12</sub>] (<strong>4</strong>) and thence [1-Ph-2-(NC<sub>5</sub>H<sub>4</sub>-2-NH<sub>2</sub>)-<i>closo</i>-1-CB<sub>9</sub>H<sub>8</sub>] (<strong>5</strong>), in which the pyridine substituent is on a boron atom α to the cluster carbon atom. This behaviour contrasts to the reactions of organyl-substituted pyridines NC<sub>5</sub>H<sub>4</sub>R to yield neutral 9-pyridine <i>arachno</i> species [6-Ph-9-(NC<sub>5</sub>H<sub>4</sub>R)-<i>arachno</i>-6-CB<sub>9</sub>H<sub>12</sub>] and thence neutral 6-pyridine <i>closo</i> species [1-Ph-6-(NC<sub>5</sub>H<sub>4</sub>R)-<i>closo</i>-1-CB<sub>9</sub>H<sub>8</sub>], in which the pyridine substituent is on a boron atom β to the cluster carbon atom. The chlorinated analogue [1-Ph-2-(NC<sub>5</sub>H<sub>4</sub>-2-NH<sub>2</sub>)-4-Cl-<i>closo</i>-1-CB<sub>9</sub>H<sub>7</sub>] (<strong>7</strong>) is also identified as a minor by-product from the reaction system. Reaction of anion <strong>1</strong> with NC<sub>5</sub>H<sub>4</sub>-4-NH<sub>2</sub> does not proceed further than [6-Ph-9-(NC<sub>5</sub>H<sub>4</sub>-4-NH<sub>2</sub>)-<i>arachno</i>-6-CB<sub>9</sub>H<sub>12</sub>] (<strong>8</strong>). The 2-NH<sub>2</sub> compounds <strong>4</strong>, <strong>5</strong> and <strong>7</strong> exhibit intramolecular BH-HN dihydrogen bonding, whereas the 4-NH<sub>2</sub> compound <strong>8</strong> exhibits an intermolecular BH-HN dihydrogen-bonded network that involves inversion-related pairs of dihydrogen-bonded chains. <p>

Title:Polyhedral Monocarbaborane Chemistry. Functionality and Isomerism: Reactions of the [6-Ph-nido-6-CB9H11]- Anion with Aminopyridines NC5H4NH2 to Yield Neutral arachno and closo Ten-Vertex Monocarbaborane Derivatives
Creators:
Bullen, Neil J.
Kennedy, John D.
Uncontrolled Keywords:Dihydrogen bonding, Crystal and molecular structure, X-Ray diffraction, Monocarbaboranes, Boranes, Pyridine adducts, Amine-functionalised carbaboranes, 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. 1873-1890
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20051873UNSPECIFIED
ID Code:2445
Item Type:Article
Deposited On:06 Feb 2009 17:18
Last Modified:06 Feb 2009 16:18

Citation

Bullen, Neil J.; Kennedy, John D. (2005) Polyhedral Monocarbaborane Chemistry. Functionality and Isomerism: Reactions of the [6-Ph-nido-6-CB9H11]- Anion with Aminopyridines NC5H4NH2 to Yield Neutral arachno and closo Ten-Vertex Monocarbaborane Derivatives. Collection of Czechoslovak Chemical Communications, 70 (11). pp. 1873-1890. ISSN 0010-0765

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