Synthesis and Properties of a Kinetically Stabilized 9-Silaphenanthrene#
- Norihiro Tokitoh ,
- Akihiro Shinohara ,
- Takeshi Matsumoto ,
- Takahiro Sasamori ,
- Nobuhiro Takeda , and
- Yukio Furukawa
View Author Information
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan, and Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
Reaction of 9-bromo-9,10-dihydro-9-silaphenanthrene (6) with lithium diisopropylamide (LDA) in THF at room temperature afforded kinetically stabilized 9-silaphenanthrene 1a bearing an efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt). 9-Silaphenanthrene 1a was isolated as pale yellow crystals, and the structure of 1a was completely determined by spectroscopic and X-ray crystallographic analyses. The 1H and 13C NMR chemical shifts corresponding to the 9-silaphenanthrene ring of 1a were observed in a typical aromatic region, while the central silicon atom showed the characteristic signal at 86.9 ppm in the 29Si NMR in C6D6. The 9-silaphenanthrene ring of 1a showed completely planar geometry, indicating that 9-silaphenanthrene has a delocalized 14π-electron system as an aromatic compound. In spite of its high thermal stability, 1a still has high reactivity at the 9,10-position toward small reagents such as H2O.
#
Dedicated to the late Prof. Yoshihiko Itoh.
*
Corresponding author. Tel: +81-774-38-3200. Fax: +81-774-38-3209. E-mail: [email protected]
§
Kyoto University.
†
Waseda University.
Cited By
This article is cited by 35 publications.
- Harald Stueger, Bernd Hasken, Michael Haas, Martin Rausch, Roland Fischer, and Ana Torvisco . Photoinduced Brook-Type Rearrangement of Acylcyclopolysilanes. Organometallics 2014, 33 (1) , 231-239. https://doi.org/10.1021/om4009845
- Lauren G. Mercier, Shunsuke Furukawa, Warren E. Piers, Atsushi Wakamiya, Shigehiro Yamaguchi, Masood Parvez, Ross W. Harrington, and William Clegg . Design, Synthesis, and Characterization of Functionalized Silepins: High Quantum Yield Blue Emitters. Organometallics 2011, 30 (6) , 1719-1729. https://doi.org/10.1021/om2000597
- Dumitru Ghereg, Heinz Gornitzka, Jean Escudié, and Sonia Ladeira . The Reactivity of Phosphagermaallene Tip(t-Bu)Ge═C═PMes* with Doubly and Triply Bonded Nitrogen Compounds. Inorganic Chemistry 2010, 49 (22) , 10497-10505. https://doi.org/10.1021/ic1014913
- Yoshiyuki Mizuhata, Naoya Noda, and Norihiro Tokitoh. Generation of Stannabenzenes and Their Properties. Organometallics 2010, 29 (21) , 4781-4784. https://doi.org/10.1021/om100382n
- Yusuke Tanabe, Yoshiyuki Mizuhata and Norihiro Tokitoh. Synthesis and Structure of a Heavier Congener of Biphenyl: 1,1′-Disila-4,4′-biphenyl. Organometallics 2010, 29 (4) , 721-723. https://doi.org/10.1021/om901095w
- Shuhei Ozaki, Takahiro Sasamori and Norihiro Tokitoh. Synthesis of a 1-Hydrosilene Stable in Solution and Its Unique Properties. Organometallics 2008, 27 (10) , 2163-2165. https://doi.org/10.1021/om8001334
- Takeshi Matsumoto, Takahiro Sasamori, Kazunobu Sato, Takeji Takui and Norihiro Tokitoh. Reduction of a Kinetically Stabilized Silabenzene Leading to the Formation of the Corresponding Anion Radical Species. Organometallics 2008, 27 (3) , 305-308. https://doi.org/10.1021/om701060a
- Deepthi Jose, Chandra Chowdhury, Ayan Datta. A Vision on Organosilicon Chemistry and Silicene. 2018,,, 1-21. https://doi.org/10.1007/978-3-319-99964-7_1
- , . Silicene. 2018,,https://doi.org/10.1007/978-3-319-99964-7
- Shintaro Ishida, Yushi Kato, Takeaki Iwamoto. A 1,2-Dibromosilene: Generation, Spectroscopic Observation, and Isomerization to a Silacyclohexane via Facile 1,2-Bromine Shift. Chemistry Letters 2017, 46 (8) , 1155-1157. https://doi.org/10.1246/cl.170409
- Michael Haas, Judith Radebner, Christoph Winkler, Roland Fischer, Ana Torvisco, Harald Stueger. Isolable endocyclic silenes by thermal Brook rearrangement. Journal of Organometallic Chemistry 2017, 830 , 131-140. https://doi.org/10.1016/j.jorganchem.2016.12.019
- Yoshiyuki Mizuhata, Norihiro Tokitoh. Silaaromatics and Related Compounds. 2017,,, 619-641. https://doi.org/10.1016/B978-0-12-801981-8.00010-1
- . Organosilicon Compounds. 2017,,https://doi.org/
- Benedikt Niepötter, Dietmar Stalke. X-Ray Crystallography of Organosilicon Compounds (Electron Density and Chemical Bonding in Organosilicon Compounds). 2017,,, 3-58. https://doi.org/10.1016/B978-0-12-814213-4.00001-0
- . Organosilicon Compounds. 2017,,https://doi.org/
- Shintaro Ishida, Takashi Abe, Fumiya Hirakawa, Tomoyuki Kosai, Katsuhiro Sato, Mitsuo Kira, Takeaki Iwamoto. Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol. Chemistry - A European Journal 2015, 21 (43) , 15100-15103. https://doi.org/10.1002/chem.201501478
- Michael Haas, Roland Fischer, Lukas Schuh, Robert Saf, Ana Torvisco, Harald Stueger. Photoinduced Rearrangement of Aryl-Substituted Acylcyclohexasilanes. European Journal of Inorganic Chemistry 2015, 2015 (6) , 997-1004. https://doi.org/10.1002/ejic.201403122
- Yoshiyuki Mizuhata, Koji Inamura, Norihiro Tokitoh. Coordination chemistry of 9-sila- and 9-germa-phenanthrenes — unique coordination modes in their metallene complexes. Canadian Journal of Chemistry 2014, 92 (6) , 441-446. https://doi.org/10.1139/cjc-2013-0501
- Soichiro Kyushin, Shintaro Ishida, Akihiro Tsurusaki, Kyohei Otsuka. Effect of Ring Sizes of Cyclooligosilanes on Construction of Organosilicon Clusters. Journal of Synthetic Organic Chemistry, Japan 2014, 72 (11) , 1290-1297. https://doi.org/10.5059/yukigoseikyokaishi.72.1290
- Jiangxi Chen, Guochen Jia. Recent development in the chemistry of transition metal-containing metallabenzenes and metallabenzynes. Coordination Chemistry Reviews 2013, 257 (17-18) , 2491-2521. https://doi.org/10.1016/j.ccr.2013.01.014
- Norihiro Tokitoh, Yoshiyuki Mizuhata, Satoshi Morikawa. SYNTHESIS OF 1,4-PHOSPHASILACYCLOHEXA-2,5-DIENES BEARING HYDROGEN OR CHLORINE ATOMS ON THE SILICON ATOMS. HETEROCYCLES 2012, 86 (2) , 1621. https://doi.org/10.3987/COM-12-S(N)114
- Tsukasa Matsuo, Katsunori Suzuki, Tomohide Fukawa, Baolin Li, Mikinao Ito, Yoshiaki Shoji, Takashi Otani, Liangchun Li, Megumi Kobayashi, Makoto Hachiya, Yoshiyuki Tahara, Daisuke Hashizume, Takeo Fukunaga, Aiko Fukazawa, Yongming Li, Hayato Tsuji, Kohei Tamao. Synthesis and Structures of a Series of Bulky “Rind-Br” Based on a Rigid Fused-Ring s -Hydrindacene Skeleton. Bulletin of the Chemical Society of Japan 2011, 84 (11) , 1178-1191. https://doi.org/10.1246/bcsj.20110090
- Yoshiyuki Mizuhata, Norihiro Tokitoh. Chemistry of Aromatic Compounds Containing a Heavier Group 14 Element. Journal of Synthetic Organic Chemistry, Japan 2011, 69 (6) , 691-704. https://doi.org/10.5059/yukigoseikyokaishi.69.691
- . Heavy Analogs of Aromatic Compounds. 2010,,, 335-414. https://doi.org/10.1002/9780470669266.ch6
- Vladimir Ya. Lee, Akira Sekiguchi. Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb. 2010,,https://doi.org/
- Yoshiyuki Mizuhata, Akihiro Shinohara, Yusuke Tanabe, Norihiro Tokitoh. Cycloaddition Reactions of Kinetically Stabilized 9-Silaanthrancene with Polycyclic Aromatic Hydrocarbons. Chemistry - A European Journal 2009, 15 (34) , 8405-8408. https://doi.org/10.1002/chem.200901290
- Yoshiyuki Mizuhata, Norihiro Tokitoh. Reactions of a kinetically stabilized 2-stannanaphthalene with elemental sulfur and selenium: synthesis of novel cyclic chalcogenides containing a tin atom. Journal of Sulfur Chemistry 2009, 30 (3-4) , 385-392. https://doi.org/10.1080/17415990903033368
- Norihiro Tokitoh, Koji Inamura, Yoshiyuki Mizuhata. Reaction of 9-Germaphenanthrene with Dimethyl Acetylenedicarboxylate: Unexpected Formation of a 1,2-Oxagermolane Derivative. HETEROCYCLES 2009, 77 (2) , 811. https://doi.org/10.3987/COM-08-S(F)82
- Yusuke Tanabe, Yoshiyuki Mizuhata, Norihiro Tokitoh. Mechanistic Investigation of the Hydration Reaction of [Cr(η 6 -silabenzene)(CO) 3 ]: Hydrido(silacyclohexadienyl)chromium Complex as an Intermediate. Chemistry Letters 2008, 37 (7) , 720-721. https://doi.org/10.1246/cl.2008.720
- Toru Oikawa, Norio Nakata, Takeshi Matsumoto, Yoshio Kabe, Akira Sekiguchi. Photochemical reaction of silyl-substituted 1,4-disila(dewar-benzene) with isocyanide and phenylacetylene. Heteroatom Chemistry 2008, 19 (1) , 87-92. https://doi.org/10.1002/hc.20411
- P. Norris. Six-membered Rings with One Other Element. 2008,,, 1049-1066. https://doi.org/10.1016/B978-008044992-0.00614-3
- . Comprehensive Heterocyclic Chemistry III. 2008,,https://doi.org/
- J. Parr. Carbon, silicon, germanium, tin and lead. Annual Reports Section "A" (Inorganic Chemistry) 2008, 104 , 97. https://doi.org/10.1039/b716566h
- Yoshiyuki Mizuhata, Takahiro Sasamori, Noriyoshi Nagahora, Yasuaki Watanabe, Yukio Furukawa, Norihiro Tokitoh. Synthesis and properties of stable 2-metallanaphthalenes of heavier group 14 elements. Dalton Transactions 2008, 33 (33) , 4409. https://doi.org/10.1039/b718193k
- Vladimir Ya. Lee, Akira Sekiguchi. Cyclic polyenes of heavy group 14 elements: new generation ligands for transition-metal complexes. Chemical Society Reviews 2008, 37 (8) , 1652. https://doi.org/10.1039/b800580j