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Doubly Bonded Silicon Compounds Showing Intramolecular Charge-Transfer Transitions

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Chemical Science of π-Electron Systems

Abstract

Recent study of doubly bonded silicon compounds showing intramolecular charge-transfer transition was reviewed. Trialkylaryldisilenes having 1-naphthyl, 9-phenanthyl, or 9-anthryl substituent were synthesized. X-ray diffraction analysis shows that π(Si=Si) and π(aryl) systems in the trialkylaryldisilenes are almost perpendicular to each other suggesting no significant conjugative interactions between two π systems, but they exhibit intramolecular charge-transfer (ICT) transitions from π(Si=Si) to π*(aryl). Especially, 9-anthryltrialkyldisilene shows a distinct ICT band at 525 nm, which redshifts to 535 nm in more polar 1,2-dichlorobenzene. Reaction of the anthryldisilene gives the corresponding [2 + 1] cycloadduct, disilacyclopropanimine, which undergoes further isomerization to give 3-silylene-2-silaaziridine with 9-anthryl substituent as a novel exocyclic silene. The anthrylsilene shows also a distinct ICT transition from π(Si=C) to π*(aryl). The high energy levels of π(Si=Si) and π(Si=C) and the low-lying π*(aryl) would be responsible for the distinct ICT band of the disilenes and the silene.

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References

  1. West R, Fink MJ, Michl J (1981) Tetramesityldisilene, a stable compound containing a silicon-silicon double bond. Science 214:1343–1344

    Article  CAS  Google Scholar 

  2. Brook AG, Abdesaken F, Gutekunst B, Gutekunst G, Kallury RK (1981) A solid silaethene: isolation and characterization. J Chem Soc Chem Commun 17:191

    Google Scholar 

  3. Brook AG, Nyburg SC, Abdesaken F, Gutekunst B, Gutekunst G, Kallury RKMR, Poon YC, Chang Y-M, Wong-Ng W (1982) Stable solid sitalethylene. J Am Chem Soc 104:5667–5672

    Article  CAS  Google Scholar 

  4. Okazaki R, West R (1996) Chemistry of stable disilenes. Adv Organomet Chem 39:231–273

    CAS  Google Scholar 

  5. Müller T, Ziche W, Auner N (1998) Silicon-carbon and silicon-nitrogen multiply bonded compounds. In: Rappoport Z, Apeloig Y (eds) The chemistry of organic silicon compounds. Wiley, Chichester, pp 857–1062

    Chapter  Google Scholar 

  6. Weidenbruch M (2001) Recent advances in the chemistry of silicon-silicon multiple bonds. In: Rappoport Z, Apeloig Y (eds) Chemistry of Organic Silicon Compounds, vol 3. Wiley, Chichester, pp 391–428

    Chapter  Google Scholar 

  7. Lee VY, Sekiguchi A (2004) Heteronuclear heavy alkenes E = E’ (E, E’=Group 14 Elements): Germasilenes, silastannenes, germastannenes…Next stop? Organometallics 23:2822–2823

    Article  CAS  Google Scholar 

  8. Kira M, Iwamoto T (2006) Progress in the chemistry of stable disilenes. Adv Organomet Chem 54:73–148

    CAS  Google Scholar 

  9. Scheschkewitz D (2011) The versatile chemistry of disilenides: Disila analogues of vinyl anions as synthons in low-valent silicon chemistry. Chem Lett 40:2–11

    Article  CAS  Google Scholar 

  10. Ottosson H, Eklöf AM (2008) Silenes: Connectors between classical alkenes and nonclassical heavy alkenes. Coord Chem Rev 252:1287–1314

    Article  CAS  Google Scholar 

  11. Scheschkewitz D (2009) Anionic reagents with silicon-containing double bonds. Chem Eur J 15:2476–2485

    Article  CAS  Google Scholar 

  12. Lee VY, Sekiguchi A, Escudié J, Ranaivonjatovo H (2010) Heteronuclear double bonds E=E’ (E=heavy group 14, E’=group 13-16 element). Chem Lett 39:312–318

    Article  CAS  Google Scholar 

  13. Sasamori T, Tokitoh N (2013) A new family of multiple-bond compounds between heavier group 14 elements. Bull Chem Soc Jpn 86:1005–1021

    Article  CAS  Google Scholar 

  14. Iwamoto T, Ishida S (2014) Multiple bonds to silicon: recent advances in synthesis, structure, and functions of stable disilenes. In: Scheschkewitz D (ed) Functional molecular silicon compounds II low oxidation state. Structure and Bonding, vol 156. Springer, New York, pp 125–202

    Google Scholar 

  15. Carter EA, Goddard WA III (1986) Relation between singlet-triplet gaps and bond energies. J Phys Chem 90:998–1001

    Article  CAS  Google Scholar 

  16. Trinquier G, Malrieu J-P (1987) Nonclassical distortions at multiple bonds. J Am Chem Soc 109:5303–5315

    Article  CAS  Google Scholar 

  17. Malrieu J-P, Trinquier G (1989) Trans bending at double bonds. Occurrence and extent. J Am Chem Soc 111:5916–5921

    Article  CAS  Google Scholar 

  18. Karni M, Apeloig Y (1990) Substituent effects on the geometries and energies of the Si=Si double bond. J Am Chem Soc 112:8589–8590

    Article  CAS  Google Scholar 

  19. Jacobsen H, Ziegler T (1994) Nonclassical double bonds in ethylene analogues: influence of Pauli repulsion on trans bending and π-bond strength. A density functional study. J Am Chem Soc 114:3667–3679

    Article  Google Scholar 

  20. Sekiguchi A, Maruki I, Ebata K, Kabuto C, Sakurai H (1991) High-pressure synthesis, structure and novel photochemical reactions of 7,7,8,8-tetramethyl-7,8-disilabicyclo[2.2.2]octa-2,5-diene. J Chem Soc, Chem Commun 27:341–343

    Google Scholar 

  21. Tokitoh N (2004) New progress in the chemistry of stable metallaaromatic compounds of heavier group 14 elements. Acc Chem Res 37:86–94

    Article  CAS  Google Scholar 

  22. Nguyen T-I, Scheschkewitz D (2005) Activation of a Si=Si bond by η1-coordination to a transition metal. J Am Chem Soc 127:10174–10175

    Article  CAS  Google Scholar 

  23. Fukawaza A, Li Y, Yamaguchi S, Tsuji H, Tamao K (2007) Coplanar oligo(p-phenylenedisilenylene)s based on the octaethyl-substituted s-hydrindacenyl group. J Am Chem Soc 129:14164–14165

    Article  Google Scholar 

  24. Bejan I, Scheschkewitz D (2007) Two Si-Si double bonds connected by a phenylene bridge. Angew Chem Int Ed 46:5783–5786

    Article  CAS  Google Scholar 

  25. Sasamori T, Yuasa A, Hosoi Y, Furukawa Y, Tokitoh N (2008) 1,2-Bis(ferrocenyl)disilene: a multistep redox system with an Si=Si double bond. Organometallics 27:3325–3327

    Article  CAS  Google Scholar 

  26. Yuasa A, Sasamori T, Hosoi Y, Furukawa Y, Tokitoh N (2009) Synthesis and properties of stable 1,2-bis(metallocenyl)disilenes: novel d–π conjugated systems with a Si=Si double bond. Bull Chem Soc Jpn 82(7):793–805

    Article  CAS  Google Scholar 

  27. Sato T, Mizuhata Y, Tokitoh N (2010) 1,2-Dialkynyldisilenes: silicon analogues of (E)-enediyne. Chem Commun 46:4402–4404

    Article  CAS  Google Scholar 

  28. Tamao K, Kobayashi M, Matsuo T, Furukawa S, Tsuji H (2012) The first observation of electroluminescence from di(2-naphthyl)disilene, an Si=Si double bond-containing π-conjugated compound. Chem Commun 48:1030–1032

    Article  CAS  Google Scholar 

  29. Kinjo R, Ichinohe M, Sekiguchi A, Takagi N, Sumimoto M, Nagase S (2007) Reactivity of a disilyne RSi ≡ SiR (R=SiiPr[CH(SiMe3)2]2 toward π-bonds: Stereospecific addition and a new route to an isolable 1,2-disilabenzene. J Am Chem Soc 129:7766–7767

    Article  CAS  Google Scholar 

  30. Han JS, Sasamori T, Mizuhata Y, Tokitoh N (2010) Reactivity of an aryl-substituted silicon-silicon triple bond: 1,2-disilabenzenes from the reactions of a 1,2-diaryldisilyne with alkynes. Dalton Trans 39(39):9238–9240

    Article  CAS  Google Scholar 

  31. Takeuchi K, Ichinohe M, Sekiguchi A (2008) Reactivity of the disilyne RSi ≡ SiR (R=SiiPr[CH(SiMe3)2]2) toward silylcyanide: Two pathways to form the bis-adduct [RSiSiR(CNSiMe3)2] with some silaketenimine character and a 1,4-diaza-2,3-disilabenzene analogue. J Am Chem Soc 130:16848–16849

    Article  CAS  Google Scholar 

  32. Takeuchi K, Ichinohe M, Sekiguchi A, Guo J-D, Nagase S (2010) Reactivity of the disilyne RSi≡SiR (R=SiiPr[CH(SiMe3)2]2) toward bis(silylcyanide) forming a 1,4-diaza-2,3-disilabenzene analog. J Phys Org Chem 23:390–394

    Google Scholar 

  33. Iwamoto T, Kobayashi M, Uchiyama K, Sasaki S, Nagendran S, Isobe H, Kira M (2009) Anthryl-substituted trialkyldisilene showing distinct intramolecular charge-transfer transition. J Am Chem Soc 2009:3156–3157

    Article  Google Scholar 

  34. Iwamoto T, Ohnishi N, Akasaka N, Ohno K, Ishida S (2013) Anthryl-substituted 3-silylene-2-silaaziridine obtained by isomerization of disilacyclopropanimine: an exocyclic silene showing a distinct intramolecular charge transfer transition. J Am Chem Soc 135(29):10606–10609

    Article  CAS  Google Scholar 

  35. Kira M, Ishida S, Iwamoto T, Kabuto C (1999) The first isolable dialkylsilylene. J Am Chem Soc 121:9722–9723

    Article  CAS  Google Scholar 

  36. Shizuka H, Obuchi H, Ishikawa M, Kumada M (1984) Photochemical and photophysical behaviour of phenylsilanes and naphthylsilanes. J Chem Soc Faraday Trans 80:383–401

    Article  CAS  Google Scholar 

  37. Yokelson HB, Millevolte AJ, Haller KJ, West R (1987) The synthesis and molecular structure of a disilacyclpropanimine. J Chem Soc Chem Commun 23:1605–1606

    Article  Google Scholar 

  38. Majumdar M, Huch V, Bejan I, Meltzer A, Scheschkewitz D (2013) Reversible, complete cleavage of Si=Si double bonds by isocyanide insertion. Angew Chem Int Ed 52:3516–3520

    Article  CAS  Google Scholar 

  39. Brook AG, Kong YK, Saxena AK, Sawyer JF (1988) Silaaziridines from the reaction of isonitrile with stable silenes. Organometallics 7:2245–2247

    Article  CAS  Google Scholar 

  40. Brook AG, Saxena AK, Sawyer JF (1989) 1-Sila-3-azacyclobutanes: the insertion of isocyanides into silaaziridines. Organometallics 8:850–852

    Article  CAS  Google Scholar 

  41. Driess M, Pritzkow H (1993) A novel type of oligofunctional macroheterocycle by reaction of silylidene-phosphane and -arsanes with 1,6-diisocyanohexane. J Chem Soc, Chem Commun 29:1585–1587

    Google Scholar 

  42. Wiberg N, Wagner G, Müller G (1985) Isolation and structure of a stable molecule containing a silicon-carbon double bond. Angew Chem Int Ed Engl 24:229–230

    Article  Google Scholar 

  43. Reichardt C, Welton T (2011) Solvent and solvent effects in organic chemistry. Wiley-VCH, New York

    Google Scholar 

  44. Bendikov M, Kravchenko V, Apeloig Y, Becker JY (2004) The first electrochemical study of a silene. An unusually low oxidation potential, comparable to those of strong organic π-electron donors. Organometallics 23:921–923

    Article  CAS  Google Scholar 

  45. Ohno K, Maeda S (2004) A scaled hypersphere search method for the topography of reaction pathways on the potential energy surface. Chem Phys Lett 384:277–282

    Article  CAS  Google Scholar 

  46. Ohno K, Maeda S (2006) Global reaction route mapping on potential energy surfaces of formaldehyde, formic acid, and their metal substituted analogues. J Phys Chem A 110:8933–8941

    Article  CAS  Google Scholar 

  47. Maeda S, Ohno K (2007) Structures of water octamers (H2O)8: Exploration on ab initio potential energy surfaces by the scaled hypersphere search method. J Phys Chem A 111:4527–4534

    Article  CAS  Google Scholar 

  48. Eklöf AM, Guliashvili T, Ottosson H (2008) Relation between the π-contribution to reversed Si=C bond polarization and the reaction profile for the thermolytic formation of silenes. Organometallics 27:5203–5211

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan

    Takeaki Iwamoto

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  1. Takeaki Iwamoto
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Correspondence to Takeaki Iwamoto .

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Editors and Affiliations

  1. Foundation for Advancement of International Science, Tsukuba, Japan

    Takeshi Akasaka

  2. Kyoto University, Kyoto, Japan

    Atsuhiro Osuka

  3. Department of Chemistry and Nano Science,, Ewha Womans University, Seoul, Korea (Republic of)

    Shunichi Fukuzumi

  4. Nagoya Institute of Technology, Nagoya, Japan

    Hideki Kandori

  5. Osaka University, Suita, Japan

    Yoshio Aso

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Iwamoto, T. (2015). Doubly Bonded Silicon Compounds Showing Intramolecular Charge-Transfer Transitions. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_22

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