1H NMR studies on the interactions of acyclic polyethers with dimethyltin dichloride in aromatic solvents.

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概要

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• The interactions between various acyclic polyethers, RO(CH<SUB>2</SUB>CH<SUB>2</SUB>O)<I><SUB>n</SUB></I>R′(R, R′=CH<SUB>3</SUB>, Ph), and dimethyltin dichloride (DMTC) in aromatic solvents have been studied by means of <SUP>1</SUP>H NMR spectroscopy. On the basis of a continuous variation method, the formation of the 1 : 1 complexes between glymes, CH<SUB>3</SUB>O(CH<SUB>2</SUB>CH<SUB>2</SUB>O)<I><SUB>n</SUB></I>CH<SUB>3</SUB>(<I>n</I>=2, 3, 4), and DMTC was revealed in benzene. The <SUP>2</SUP><I>J</I>(<SUP>119</SUP>Sn–CH<SUB>3</SUB>) values suggested distorted <I>trans</I>-octahedral configurations for these complexes. From the statistical consideration of stability constants, it was found that the coordination occurred virtually through neighboring two oxygen atoms in these complexes. DMTC gave the complexes of both 1 : 1 and 1 : 2 glyme/DMTC stoichiometry with glymes (<I>n</I>=5, 6) in benzene and with all glymes employed here in toluene and 1-chloronaphthalene. Coexistence of 1 : 1 and 1 : 2 species was also encountered for PhO(CH<SUB>2</SUB>CH<SUB>2</SUB>O)<I><SUB>n</SUB></I>CH<SUB>3</SUB> (<I>n</I>=3, 4, 5), whereas no appreciable interaction was observed between PhO(CH<SUB>2</SUB>CH<SUB>2</SUB>O)<I><SUB>n</SUB></I>Ph (<I>n</I>=2, 3, 4) and DMTC. On the basis of these observations, the additional formation of the 1 : 2 complexes was assumed to be caused by the bulkiness of polyethers.

• 公益社団法人 日本化学会の論文

著者

• Otera Junzo

  Okayama University of Science

• Shiomi Tadashi

  Okayama University of Science

• Murakami Kazuhiko

  Okayama University of Science

• Kawasaki Yoshikane

  Department of Petroleum Chemistry, Osaka University

関連論文

• 1H NMR studies on the interactions of acyclic polyethers with dimethyltin dichloride in aromatic solvents.

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