Building a Picture of Heteroborane Isomerisation: Synthesis and Characterisation of the 10-(Dialkyl- sulfane)-7,8-diphenyl-7,8-dicarba-nido-undecaboranes 7,8-Ph2-10-L-7,8-nido-C2B9H10 (L = SMe2, SMeEt, SEt2) and of Intermediate and Isomerised Products Arising from Metallation of the First of These

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Title:Building a Picture of Heteroborane Isomerisation: Synthesis and Characterisation of the 10-(Dialkyl- sulfane)-7,8-diphenyl-7,8-dicarba-nido-undecaboranes 7,8-Ph2-10-L-7,8-nido-C2B9H10 (L = SMe2, SMeEt, SEt2) and of Intermediate and Isomerised Products Arising from Metallation of the First of These
Creators:
Dunn, Shirley
Garrioch, Rhona M.
Rosair, Georgina M.
Smith, Lorraine
Welch, Alan J.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 64, 6, pp. 1013-1027
Uncontrolled Keywords:Isomerisation, Metallacarboranes, Molybdenacarboranes, X-Ray diffraction, Crystal structure, Carboranes, NMR spectroscopy, <sup>1</sup>H, <sup>11</sup>B

Abstract

Three new, substituted, <i>nido</i> carboranes, 7,8-Ph<sub>2</sub>-10-(SMe<sub>2</sub>)-7,8-<i>nido</i>-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub> (<strong>1a</strong>), 7,8-Ph<sub>2</sub>-10- (SMeEt)-7,8-<i>nido</i>-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub> (<strong>1b</strong>) and 7,8-Ph<sub>2</sub>-10-(SEt<sub>2</sub>)-7,8-<i>nido</i>-C<sub>2</sub>B<sub>9</sub>H<sub>10</sub> (<strong>1c</strong>) have been synthesised and characterised, including a crystallographic study of the first. Deprotonation of <strong>1a</strong> followed by treatment with (MeCN)<sub>2</sub>(CO)<sub>2</sub>MoBr(η-C<sub>3</sub>H<sub>5</sub>) at 0 °C affords the non-icosahedral 1,2-Ph<sub>2</sub>-4-(SMe<sub>2</sub>)-5-(η-C<sub>3</sub>H<sub>5</sub>)-5,5-(CO)<sub>2</sub>-5,1,2-<i>closo</i>-MoC<sub>2</sub>B<sub>9</sub>H<sub>8</sub> (<strong>2a</strong>), which on subsequent warming transforms into icosahedral 2,8-Ph<sub>2</sub>-5-(SMe<sub>2</sub>)-1-(η-C<sub>3</sub>H<sub>5</sub>)-1,1-(CO)<sub>2</sub>-1,2,8-<i>closo</i>- MoC<sub>2</sub>B<sub>9</sub>H<sub>8</sub> (<strong>3a</strong>). It is argued that under the conditions of these rearrangements the B-S bond is likely to remain intact, and consequently that the identity of the SMe<sub>2</sub>-labelled boron atom in <strong>3a</strong> affords useful experimental information on the course of the isomerisation. <p>

Title:Building a Picture of Heteroborane Isomerisation: Synthesis and Characterisation of the 10-(Dialkyl- sulfane)-7,8-diphenyl-7,8-dicarba-nido-undecaboranes 7,8-Ph2-10-L-7,8-nido-C2B9H10 (L = SMe2, SMeEt, SEt2) and of Intermediate and Isomerised Products Arising from Metallation of the First of These
Creators:
Dunn, Shirley
Garrioch, Rhona M.
Rosair, Georgina M.
Smith, Lorraine
Welch, Alan J.
Uncontrolled Keywords:Isomerisation, Metallacarboranes, Molybdenacarboranes, X-Ray diffraction, Crystal structure, Carboranes, NMR spectroscopy, <sup>1</sup>H, <sup>11</sup>B
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:64
Number:6
Page Range:pp. 1013-1027
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19991013UNSPECIFIED
ID Code:1535
Item Type:Article
Deposited On:06 Feb 2009 17:10
Last Modified:06 Feb 2009 16:10

Citation

Dunn, Shirley; Garrioch, Rhona M.; Rosair, Georgina M.; Smith, Lorraine; Welch, Alan J. (1999) Building a Picture of Heteroborane Isomerisation: Synthesis and Characterisation of the 10-(Dialkyl- sulfane)-7,8-diphenyl-7,8-dicarba-nido-undecaboranes 7,8-Ph2-10-L-7,8-nido-C2B9H10 (L = SMe2, SMeEt, SEt2) and of Intermediate and Isomerised Products Arising from Metallation of the First of These. Collection of Czechoslovak Chemical Communications, 64 (6). pp. 1013-1027. ISSN 0010-0765

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