CHEMISTRY OF OXOPHILIC TRANSITION-METALS .2. NOVEL DERIVATIVES OF TITANOCENE AND ZIRCONOCENE
CHEMISTRY OF OXOPHILIC TRANSITION-METALS .2. NOVEL DERIVATIVES OF TITANOCENE AND ZIRCONOCENE
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DOI：
10.1021/om00143a019
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发表时间：
1986-12-01
期刊：
影响因子：
2.8
通讯作者：
ASHWORTH, TV
中科院分区：
文献类型：
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作者：
CUENCA, T;HERRMANN, WA;ASHWORTH, TV
用1.5当量的钠汞齐（Na/Hg）还原二氯双（1 j 5-dibis）钛（IV）（3），得到组成为[（776-6 5）（μ-1）] 2（μ-5：5-10 8）的双核t; 5：7 j 5-富瓦烯配合物4和“二茂钛”5，产率各为40%;两种化合物均代表Ti（III）物种。氯桥络合物4在暴露于空气时发生快速氧化，从而产生Ti（IV）衍生物[（i75-C5 H5）TiCl] 2-（µ-7，-010 8）（µ-）（6）。用三乙基二氢硼氢化锂还原4干净地得到“二茂钛”5，后一种化合物代表了合成硫桥富瓦烯络合物[（-5 5）（µ-8）] 2（µ-775：75-10 8）（7）的良好起始材料。当与分子氧接触时，化合物7依次经历硫/氧交换反应;在这种情况下，形成氧代/硫桥连衍生物[（5-5 6）] 2（µ-）（µ-8）（µ-6：5-10 8）（8）。
Reduction of dichlorobis (ij5-cyclopentadienyl) titanium (IV)(3) with 1.5 equiv of sodium amalgam (Na/Hg) gives thedinuclear t; 5: 7j5-fulvalene complex 4 of composition [(776-6 5)(µ-1)] 2 (µ-5: 5-10 8) and the “titanocene” 5 in 40% yield each; both compounds represent Ti (III) species. The chloro-bridged complex 4 undergoes quick oxidation upon exposure to air, thus yielding the Ti (IV) derivative [(i75-C5H5) TiCl] 2-(µ-7,-010 8)(µ-)(6). Reduction of 4 with lithium triethylhydridoboranate cleanly gives “titanocene” 5, with the latter compound representing a good starting material for the synthesis of the sulfido-bridged fulvalene complex [(-5 5)(µ-8)] 2 (µ-775: 75-10 8)(7). Compound 7 in turn undergoes a sulfur/oxygen exchange reaction whentreated with molecular oxygen; in this case, the oxo-/sulfido-bridged derivative [(5-5 6)] 2 (µ-)(µ-8)(µ-6: 5-10 8)(8) is formed.