Metallation of aliphatic carbon atoms. IV Syntheses and characterization of the cyclopalladated complexes of 2-t-butylbenzothiazole.
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概要
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2-<I>t</I>-Butylbenzothiazole reacts with palladium(II) acetate in acetic acid to produce the cyclopalladated dimer [{Pd(CH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS)(μ-MeCO<SUB>2</SUB>)}<SUB>2</SUB>] (<B>2</B>) (C<SUB>7</SUB>H<SUB>4</SUB>NS=2-benzothiazolyl). Complex <B>2</B> shows temperature-dependent <SUP>1</SUP>H NMR spectra, which have been interpreted on the basis of the inversion motion of the acetato bridges. Metatheses of <B>2</B> with lithium chloride and sodium iodide result in the formation of the chloro- and iodo-bridged analogues, [{Pd(CH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS)(μ-Cl)}<SUB>2</SUB>] (<B>3</B>) and [{Pd(CH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS)(μ-I)}<SUB>2</SUB>] (<B>4</B>), respectively, each of which is found to be composed of cis and trans isomers. The <SUP>1</SUP>H NMR spectra of <B>3</B> and <B>4</B> depend on temperature and are ascribed to rapid exchange between the two isomers. Equimolar amounts of <B>3</B> and <B>4</B> afford a μ-chloro-μ-iodo binuclear complex, [(C<SUB>7</SUB>H<SUB>4</SUB>NS–CMe<SUB>2</SUB>CH<SUB>2</SUB>)Pd(μ-Cl)(μ-I)Pd(CH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS)]. The reaction of <B>3</B> with thallium(I) acetylacetonate [Tl(acac)] produces a mononuclear cyclopalladated complex [Pd(CH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS)(acac)]. Complexes <B>2</B> and <B>3</B> react with CO in methanol to give MeO<SUB>2</SUB>CCH<SUB>2</SUB>CMe<SUB>2</SUB>–C<SUB>7</SUB>H<SUB>4</SUB>NS, the formation of which comfirms also the cyclopalladated structure of 2-<I>t</I>-butylbenzothiazole in <B>2</B> and <B>3</B>.
- 公益社団法人 日本化学会の論文
著者
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Fuchita Yoshio
Department Of Chemistry Faculty Of Science Kyushu University Ropponmatsu
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Hiraki Katsuma
Department Of Applied Chemistry Faculty Of Engineering Nagasaki University
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Nakashima Motoharu
Department of Industrial Chemistry, Faculty of Engineering, Nagasaki University
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Hiraki Hirofumi
Department of Industrial Chemistry, Faculty of Engineering, Nagasaki University
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