Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive

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Title:Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive
Creators:
Hoque, A. K. M. M.
Shine, Henry J.
Venkatachalam, T. Krishnan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 58, 1, pp. 82-88

Abstract

Diarylmercurials (Ar<sub>2</sub>Hg) with Ar = <i>p</i>-tolyl <i>Ib</i>, <i>o</i>-tolyl <i>Ic</i>, <i>p</i>-anisyl <i>Id</i> and 2-allyloxy-4,5-dimethylphenyl <i>Ie</i>, reacted with thianthrene cation radical perchlorate (Th<sup>.+</sup>ClO<sub>4</sub><sup>-</sup>) in two stoichiometric ratios: 2 : 1 and 4 : 1 (Th<sup>.+</sup>ClO<sub>4</sub><sup>-</sup>/Ar<sub>2</sub>Hg). In the 2 : 1 ratio the products were the 5-arylthianthreniumyl perchlorates <i>IIb - IIe</i>, thianthrene (Th) and ArHg<sup>+</sup>ClO<sub>4</sub><sup>-</sup> (assayed as ArHgCl, <i>III</i>) in quantitative yields. In the 4 : 1 ratio reaction with ArHg<sup>+</sup> occurred, too, and the products were <i>IIb - IIe</i>, Th, the complex Th<sub>3</sub>Hg(ClO<sub>4</sub>)<sub>2</sub> and HgO (after workup). In contrast, Ph<sub>2</sub>Hg (<i>Ia</i>) did not react beyond the 2 : 1 stoichiometry. In the reactions with <i>Ie</i>, no evidence for formation and cyclization of free 2-allyloxy-4,5-dimethylphenyl radical was found. Reaction of and product formation from these arylmercurials, therefore, does not occur in single electron transfer steps that lead to free aryl radicals. Instead electron transfer appears to occur within a complex of Ar<sub>2</sub>Hg with Th<sup>.+</sup> from which <i>II</i> and other products are subsequently formed.

Title:Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive
Creators:
Hoque, A. K. M. M.
Shine, Henry J.
Venkatachalam, T. Krishnan
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:58
Number:1
Page Range:pp. 82-88
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19930082UNSPECIFIED
ID Code:130
Item Type:Article
Deposited On:06 Feb 2009 16:58
Last Modified:06 Feb 2009 15:58

Citation

Hoque, A. K. M. M.; Shine, Henry J.; Venkatachalam, T. Krishnan (1993) Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive. Collection of Czechoslovak Chemical Communications, 58 (1). pp. 82-88. ISSN 0010-0765

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