(4-1,5-Cyclooctadiene)(6-phosphinine)iron(0):
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- 作者：Falk Knoch ; Frank Kremer ; Uwe Schmidt ; Ulrich Zenneck ; Pascal Le Floch ; and Francois Mathey
- 刊名：Organometallics
- 出版年：1996
- 出版时间：June 11, 1996
- 年：1996
- 卷：15
- 期：12
- 页码：2713 - 2719
- 全文大小：146K
- 年卷期：v.15,no.12(June 11, 1996)
- ISSN：1520-6041
文摘
Two routes are described for the synthesis of(
4-1,5-cyclooctadiene)(6-phosphinine)iron(0) complexes. A three-component reaction of iron vapor with CODand 2-(trimethylsilyl)-4,5-dimethylphosphinine at low temperature yields 20%(COD)(2-(trimethylsilyl)-4,5-dimethylphosphinine)Fe(0) (3), whereas ligandexchange of one COD ligand of the in situprepared metal vapor product (COD)2Fe by2-(trimethylsilyl)-4,5-dimethylphosphinine or(1-2-chloro-4,5-dimethylphosphinine)Cr(CO)5gives corresponding (COD)(phosphinine)Fe(0)complexes in more than 80% isolated yield. As the phosphininederivatives are prochiral,complexation leads to the racemate of two enantiomers. Bothenantiomers are found in theunit cell of single crystalline 3 and are related by aninversion center. Complex 3 is a novelroom-temperature catalyst for the [2 + 2 + 2] cyclic additionreaction of one molecule ofbutyronitrile with two molecules of methyl propargyl ether giving up to160 mol of pyridinederivatives/mol 3. A chemically robust species, 3is an air-stable crystalline material, butexposure to oxygen in solution causes slow decomposition.
4-1,5-cyclooctadiene)(6-phosphinine)iron(0) complexes. A three-component reaction of iron vapor with CODand 2-(trimethylsilyl)-4,5-dimethylphosphinine at low temperature yields 20%(COD)(2-(trimethylsilyl)-4,5-dimethylphosphinine)Fe(0) (3), whereas ligandexchange of one COD ligand of the in situprepared metal vapor product (COD)2Fe by2-(trimethylsilyl)-4,5-dimethylphosphinine or(1-2-chloro-4,5-dimethylphosphinine)Cr(CO)5gives corresponding (COD)(phosphinine)Fe(0)complexes in more than 80% isolated yield. As the phosphininederivatives are prochiral,complexation leads to the racemate of two enantiomers. Bothenantiomers are found in theunit cell of single crystalline 3 and are related by aninversion center. Complex 3 is a novelroom-temperature catalyst for the [2 + 2 + 2] cyclic additionreaction of one molecule ofbutyronitrile with two molecules of methyl propargyl ether giving up to160 mol of pyridinederivatives/mol 3. A chemically robust species, 3is an air-stable crystalline material, butexposure to oxygen in solution causes slow decomposition.