Metallation of Aliphatic Carbon Atoms. IV. Syntheses and Characterization of the Cyclopalladated Complexes of 2-t-Butylbenzothiazole
- 1 October 1986
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 59 (10) , 3073-3077
- https://doi.org/10.1246/bcsj.59.3073
Abstract
2-t-Butylbenzothiazole reacts with palladium(II) acetate in acetic acid to produce the cyclopalladated dimer [{Pd(CH2CMe2–C7H4NS)(μ-MeCO2)}2] (2) (C7H4NS=2-benzothiazolyl). Complex 2 shows temperature-dependent 1H NMR spectra, which have been interpreted on the basis of the inversion motion of the acetato bridges. Metatheses of 2 with lithium chloride and sodium iodide result in the formation of the chloro- and iodo-bridged analogues, [{Pd(CH2CMe2–C7H4NS)(μ-Cl)}2] (3) and [{Pd(CH2CMe2–C7H4NS)(μ-I)}2] (4), respectively, each of which is found to be composed of cis and trans isomers. The 1H NMR spectra of 3 and 4 depend on temperature and are ascribed to rapid exchange between the two isomers. Equimolar amounts of 3 and 4 afford a μ-chloro-μ-iodo binuclear complex, [(C7H4NS–CMe2CH2)Pd(μ-Cl)(μ-I)Pd(CH2CMe2–C7H4NS)]. The reaction of 3 with thallium(I) acetylacetonate [Tl(acac)] produces a mononuclear cyclopalladated complex [Pd(CH2CMe2–C7H4NS)(acac)]. Complexes 2 and 3 react with CO in methanol to give MeO2CCH2CMe2–C7H4NS, the formation of which comfirms also the cyclopalladated structure of 2-t-butylbenzothiazole in 2 and 3.This publication has 8 references indexed in Scilit:
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