Synthesis and Reduction of Silyl-Substituted [5]Radialene. Characterization and Structure of a [5]Radialene Tetraanion with a Ten-Center, Fourteen-Electron π-System
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- Tsukasa Matsuo
- Department of Chemistry, University of Tsukuba Tsukuba, Ibaraki 305-8571
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- Hidetoshi Fure
- Department of Chemistry, University of Tsukuba Tsukuba, Ibaraki 305-8571
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- Akira Sekiguchi
- Department of Chemistry, University of Tsukuba Tsukuba, Ibaraki 305-8571
説明
<jats:title>Abstract</jats:title> <jats:p>The reaction of 3,3,6,6,8,8,11,11,14,14,16,16,19,19,21,21-hexadecamethyl-3,6,8,11,14,16,19,21-octasilacyclohenicosa-1,4,9,12,17-pentayne with an excess molar amount of [Mn(CO)3(Me-Cp)] in tetrahydrofuran (THF) under photochemical and refluxing conditions produced 2,2,4,4,9,9,11,11,13,13,15,15,17,17,21,21-hexadecamehyl-2,4,9,11,13,15,17,21-octasilahexacyclo[10.5.3.15,8.06,18.07,20.014,19]henicosa-1(18),5,7,12(20),14(19)-pentaene (2) as silyl-substituted [5]radialene derivative. This was reacted with lithium metal in THF to give dark red crystals of the tetralithium salt (4) of 2. The molecular structure of tetraanion of 2 with a novel ten-center, fourteen-electron π-system was established by X-ray crystallography. The tetralithium salt 4 has a monomeric structure and forms contact ion pairs (tetrakis-CIPs) in the crystals. The structural parameters of 4 are discussed in comparison with those of the neutral starting molecule 2. The structure of 4 in solution is also discussed on the basis of NMR spectroscopic data.</jats:p>
収録刊行物
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- Bulletin of the Chemical Society of Japan
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Bulletin of the Chemical Society of Japan 73 (9), 2129-2137, 2000-09-01
Oxford University Press (OUP)
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詳細情報 詳細情報について
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- CRID
- 1360846644034809728
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- NII論文ID
- 130004150754
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- ISSN
- 13480634
- 15222667
- 00092673
- 09317597
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