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Article

Synthesis and Structure of Polynuclear Indoxanes and Thalloxanes Containing Bulky m-Terphenyl Substituents

Supporting Info

S. Usman Ahmad and Jens Beckmann*

Institut f

r Chemie und Biochemie, Freie Universit

t Berlin, Fabeckstrasse 34-36, 14195 Berlin, Germany

Organometallics, 2009, 28 (24), pp 6893–6901

DOI: 10.1021/om9007967

Publication Date (Web): October 29, 2009

*Corresponding author. E-mail: beckmann@chemie.fu-berlin.de.

Abstract

Depending on the reaction conditions, the base hydrolysis of (2,6-Mes₂C₆H₃In)₂(μ-Cl)₂Cl₂ (1) in a two-layer system of aqueous NaOH/diethyl ether or toluene afforded 2,6-Mes₂C₆H₃InCl₂·H₂O (2), (2,6-Mes₂C₆H₃In)₂(μ-OH)₂Cl₂ (3), (2,6-Mes₂C₆H₃In)₃(μ-OH)₄Cl₂ (4), and (2,6-Mes₂C₆H₃In)₄(μ-OH)₈ (5), respectively, in high yields. The indoxane 5 can be regarded as a heavier and aggregated congener of arylboronic acids. An attempt at preparing (2,6-Mes₂C₆H₃Tl)₂(μ-Cl)₂Cl₂ (6) by the chlorination of 2,6-Mes₂C₆H₃Tl (prepared in situ from 2,6-Mes₂C₆H₃Li and TlCl) using SO₂Cl₂ provided the isomeric diarylthallium cation [(2,6-Mes₂C₆H₃)₂Tl]TlCl₄ (7). The exposure of crude reaction mixture consisting of 2,6-Mes₂C₆H₃Tl and LiCl to moist air surprisingly produced (2,6-Mes₂C₆H₃Tl)₂(μ-OH)₂Cl₂ (8), which reacted with hydrochloric acid to give 6. Base hydrolysis of 8 in a two-layer system of aqueous NaOH/CHCl₃ proceeded with partial cleavage of the m-terphenyl substituents and yielded the thalloxane cluster (2,6-Mes₂C₆H₃Tl)₄Tl₂(μ₃-O)₄(μ-OH)₆ (9) in moderate yield. Compounds 1−9 were characterized by X-ray crystallography.

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History

Published In Issue December 28, 2009
Article ASAPOctober 29, 2009
Received: September 11, 2009

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Article

Synthesis and Structure of Polynuclear Indoxanes and Thalloxanes Containing Bulky m-Terphenyl Substituents