Synthesis, Structure, and Reactions of Stable Titanacyclopentanes.
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概要
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Titanacyclic compounds of the formula Cp<SUP>*</SUP><SUB>2</SUB>Ti(CH<SUB>2</SUB>CH<SUB>2</SUB>C(CH<SUB>2</SUB>CHR)CH<SUB>2</SUB>) (<B>5a</B>; R=H and <B>5b</B>; R=C<SUB>6</SUB>H<SUB>5</SUB>, Cp<SUP>*</SUP>=pentamethylcyclopentadienyl), the first stable titanacyclopentanes, have been prepared by the reaction of bis(pentamethylcyclopentadienyl)titanium–ethylene complex (<B>3</B>) with methylenecyclopropanes (<B>4</B>), and their structures were determined based on both spectroscopic data and X-ray crystallography. Complex <B>5b</B> crystallized in space group <I>P</I>2<SUB>1</SUB>⁄<I>a</I>(<I>Z</I>=4) with cell constants, <I>a</I>=21.832(3), <I>b</I>=8.580(1), <I>c</I>=14.759(2) Å, β=96.81(1)°, <I>U</I>=2744.9(6) Å<SUP>3</SUP> (4261 reflections, <I>R</I>=0.053). The reaction of <B>5</B> with carbon monoxide afforded spiro[2.4]heptan-5-ones in 98% yield. The thermal decomposition of <B>5</B> has been investigated, and possible mechanisms of the reactions have been proposed based on deuterium-labeled experiments. A novel formal reductive elimination of organic ligands giving 1-phenylspiro[2.4]hexane has been observed in the thermolysis of <B>5b</B>. A structure–reactivity relationship has been discussed.
- 公益社団法人 日本化学会の論文
著者
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Mashima Kazushi
Department of Industrial Chemistry, Faculty of Engineering, Kyoto University
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Sakai Nozomu
Department of Industrial Chemistry, Faculty of Engineering, Kyoto University