logo

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Organometallics 2011, 30, 13, 3475-3478
RETURN TO ISSUEPREVCommunicationNEXT

Synthesis and Striking Reactivity of an Isolable Tetrasilyl-Substituted Trisilaallene

View Author Information
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Institute of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2 D-10623 Berlin, Germany
Tel: +81-29-853-4314. Fax: +81-29-853-4314. E-mail: [email protected]
Cite this: Organometallics 2011, 30, 13, 3475–3478
Publication Date (Web):June 14, 2011
https://doi.org/10.1021/om200405e
Copyright © 2011 American Chemical Society
RIGHTS & PERMISSIONS
Article Views
1168
Altmetric
-
Citations
41
LEARN ABOUT THESE METRICS

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

Read OnlinePDF (1 MB)
Get e-Alerts
Supporting Info (1)»
SUBJECTS:

Abstract

Abstract Image

The first silyl-substituted Si3-allene, namely 1,1,3,3-tetrakis(di-tert-butylmethylsilyl)trisilaallene (4), was prepared as an air- and moisture-sensitive red solid by the reaction of the dilithiosilane (tBu2MeSi)2SiLi2 with the dichlorosilylene–NHC complex :SiCl2←NHC (NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) in benzene at room temperature. Remarkably, the reaction of 4 with methanol proceeds regioselectively to form only the 3,3-dimethoxypentasilane derivative 5, in contrast to the case for a previously reported trisilaallene. In addition, 4 undergoes unprecedented thermal isomerization to tetrakis(di-tert-butylmethylsilyl)cyclotrisilene (7).

Supporting Information

ARTICLE SECTIONS
Jump To

Text, figures, and tables giving experimental procedures for 4 and 5, spectral charts of 4 and 5, computational results on 4, an MO diagram and the energy levels of 4, and an ORTEP drawing of 5. This material is available free of charge via the Internet at http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 48 publications.

  1. Srinivas Doddipatla, Zhenghai Yang, Aaron M. Thomas, Yue-Lin Chen, Bing-Jian Sun, Agnes H. H. Chang, Alexander M. Mebel, Ralf I. Kaiser. Gas Phase Synthesis of the Elusive Trisilacyclopropyl Radical (Si3H5) via Unimolecular Decomposition of Chemically Activated Doublet Trisilapropyl Radicals (Si3H7). The Journal of Physical Chemistry Letters 2020, 11 (18) , 7874-7881. https://doi.org/10.1021/acs.jpclett.0c02281
  2. Yuwen Wang, Miriam Karni, Shenglai Yao, Alexander Kaushansky, Yitzhak Apeloig, Matthias Driess. Synthesis of an Isolable Bis(silylene)-Stabilized Silylone and Its Reactivity Toward Small Gaseous Molecules. Journal of the American Chemical Society 2019, 141 (32) , 12916-12927. https://doi.org/10.1021/jacs.9b06603
  3. Priyabrata Ghana, Marius I. Arz, Uttam Chakraborty, Gregor Schnakenburg, Alexander C. Filippou. Linearly Two-Coordinated Silicon: Transition Metal Complexes with the Functional Groups M≡Si—M and M═Si═M. Journal of the American Chemical Society 2018, 140 (23) , 7187-7198. https://doi.org/10.1021/jacs.8b02902
  4. Cem B. Yildiz and David Scheschkewitz . Reactivity of Heavier Vinyl Anions [(CH3)2E═E′(CH3)]− (E, E′ = C, Si, Ge) toward Carbon Monoxide: A Computational Study. Organometallics 2017, 36 (16) , 3035-3042. https://doi.org/10.1021/acs.organomet.7b00327
  5. Tomoyuki Kosai, Shintaro Ishida, and Takeaki Iwamoto . Pentasila-1,4-diene: Homoconjugation between Si═Si Double Bonds via a SiMe2 Unit. Journal of the American Chemical Society 2017, 139 (1) , 99-102. https://doi.org/10.1021/jacs.6b11912
  6. Tao Yang, Beni B. Dangi, Aaron M. Thomas, Ralf I. Kaiser, Bing-Jian Sun, Monika Staś, and Agnes H. H. Chang . Gas-Phase Synthesis of the Elusive Trisilicontetrahydride Species (Si3H4). The Journal of Physical Chemistry Letters 2017, 8 (1) , 131-136. https://doi.org/10.1021/acs.jpclett.6b02710
  7. Gang He, Olena Shynkaruk, Melanie W. Lui, and Eric Rivard . Small Inorganic Rings in the 21st Century: From Fleeting Intermediates to Novel Isolable Entities. Chemical Reviews 2014, 114 (16) , 7815-7880. https://doi.org/10.1021/cr400547x
  8. Yun Xiong, Shenglai Yao, Gengwen Tan, Shigeyoshi Inoue, and Matthias Driess . A Cyclic Germadicarbene (“Germylone”) from Germyliumylidene. Journal of the American Chemical Society 2013, 135 (13) , 5004-5007. https://doi.org/10.1021/ja402477w
  9. Rajendra S. Ghadwal, Ramachandran Azhakar, and Herbert W. Roesky . Dichlorosilylene: A High Temperature Transient Species to an Indispensable Building Block. Accounts of Chemical Research 2013, 46 (2) , 444-456. https://doi.org/10.1021/ar300196u
  10. Katsunori Suzuki, Tsukasa Matsuo, Daisuke Hashizume, and Kohei Tamao . Room-Temperature Dissociation of 1,2-Dibromodisilenes to Bromosilylenes. Journal of the American Chemical Society 2011, 133 (49) , 19710-19713. https://doi.org/10.1021/ja209736d
  11. Tsukasa Matsuo, Naoki Hayakawa. π-Electron systems containing Si=Si double bonds. Science and Technology of Advanced Materials 2018, 19 (1) , 108-129. https://doi.org/10.1080/14686996.2017.1414552
  12. Nirmala Muthukumaran, Kavitha Velappan, Kritika Gour, Ganesan Prabusankar. N-heterocyclic carbene supported halosilylenes: New frontiers in an emerging field. Coordination Chemistry Reviews 2018, 377 , 1-43. https://doi.org/10.1016/j.ccr.2018.08.021
  13. Andreas Rammo, David Scheschkewitz. Functional Disilenes in Synthesis. Chemistry - A European Journal 2018, 24 (27) , 6866-6885. https://doi.org/10.1002/chem.201704090
  14. Vitaly Nesterov, Nora C. Breit, Shigeyoshi Inoue. Advances in Phosphasilene Chemistry. Chemistry - A European Journal 2017, 23 (50) , 12014-12039. https://doi.org/10.1002/chem.201700829
  15. Antoine Baceiredo, Tsuyoshi Kato. Multiple Bonds to Silicon (Recent Advances in the Chemistry of Silicon Containing Multiple Bonds). 2017,,, 533-618. https://doi.org/10.1016/B978-0-12-801981-8.00009-5
  16. . Organosilicon Compounds. 2017,,https://doi.org/
  17. 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
  18. . Organosilicon Compounds. 2017,,https://doi.org/
  19. S.U. Ahmad, S. Inoue. Multiple Bonding in Silicon Compounds. 2016,,, 73-89. https://doi.org/10.1016/B978-0-12-803530-6.00007-X
  20. . Efficient Methods for Preparing Silicon Compounds. 2016,,https://doi.org/
  21. Carsten Präsang, David Scheschkewitz. Reactivity in the periphery of functionalised multiple bonds of heavier group 14 elements. Chemical Society Reviews 2016, 45 (4) , 900-921. https://doi.org/10.1039/C5CS00720H
  22. Bochao Su, Rakesh Ganguly, Yongxin Li, Rei Kinjo. Isolation of an Imino-N-heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent. Angewandte Chemie 2014, 126 (48) , 13322-13325. https://doi.org/10.1002/ange.201406930
  23. Yu-Liang Shan, Wai-Leung Yim, Cheuk-Wai So. An N-Heterocyclic Silylene-Stabilized Digermanium(0) Complex. Angewandte Chemie 2014, 126 (48) , 13371-13374. https://doi.org/10.1002/ange.201408347
  24. Bochao Su, Rakesh Ganguly, Yongxin Li, Rei Kinjo. Isolation of an Imino-N-heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent. Angewandte Chemie International Edition 2014, 53 (48) , 13106-13109. https://doi.org/10.1002/anie.201406930
  25. Yu-Liang Shan, Wai-Leung Yim, Cheuk-Wai So. An N-Heterocyclic Silylene-Stabilized Digermanium(0) Complex. Angewandte Chemie International Edition 2014, 53 (48) , 13155-13158. https://doi.org/10.1002/anie.201408347
  26. Fabian Uhlemann, Ralf Köppe, Andreas Schnepf. Synthesis of Metastable Si II X 2 Solutions ( X = F, Cl). A Novel Binary Halide for Synthesis. Zeitschrift für anorganische und allgemeine Chemie 2014, 640 (8-9) , 1658-1664. https://doi.org/10.1002/zaac.201400122
  27. Megumi Kobayashi, Naoki Hayakawa, Koichi Nakabayashi, Tsukasa Matsuo, Daisuke Hashizume, Hiroyuki Fueno, Kazuyoshi Tanaka, Kohei Tamao. Highly Coplanar ( E )-1,2-Di(1-naphthyl)disilene Involving a Distinct CH–π Interaction with the Perpendicularly Oriented Protecting Eind Group. Chemistry Letters 2014, 43 (4) , 432-434. https://doi.org/10.1246/cl.131043
  28. Benedikt Niepötter, Regine Herbst-Irmer, Daniel Kratzert, Prinson P. Samuel, Kartik Chandra Mondal, Herbert W. Roesky, Paul Jerabek, Gernot Frenking, Dietmar Stalke. Experimentelle Elektronendichteuntersuchung eines Silylons. Angewandte Chemie 2014, 126 (10) , 2806-2811. https://doi.org/10.1002/ange.201308609
  29. Terry Chu, Lee Belding, Art van der Est, Travis Dudding, Ilia Korobkov, Georgii I. Nikonov. A Coordination Compound of Ge 0 Stabilized by a Diiminopyridine Ligand. Angewandte Chemie 2014, 126 (10) , 2749-2753. https://doi.org/10.1002/ange.201309421
  30. Benedikt Niepötter, Regine Herbst-Irmer, Daniel Kratzert, Prinson P. Samuel, Kartik Chandra Mondal, Herbert W. Roesky, Paul Jerabek, Gernot Frenking, Dietmar Stalke. Experimental Charge Density Study of a Silylone. Angewandte Chemie International Edition 2014, 53 (10) , 2766-2770. https://doi.org/10.1002/anie.201308609
  31. Terry Chu, Lee Belding, Art van der Est, Travis Dudding, Ilia Korobkov, Georgii I. Nikonov. A Coordination Compound of Ge 0 Stabilized by a Diiminopyridine Ligand. Angewandte Chemie International Edition 2014, 53 (10) , 2711-2715. https://doi.org/10.1002/anie.201309421
  32. Christoph Marschner. Oligosilanes. 2013,,, 163-228. https://doi.org/10.1007/430_2013_103
  33. . Functional Molecular Silicon Compounds I. 2014,,https://doi.org/10.1007/978-3-319-03620-5
  34. Carsten Präsang, David Scheschkewitz. Silyl Anions. 2013,,, 1-47. https://doi.org/10.1007/430_2013_104
  35. . Functional Molecular Silicon Compounds II. 2014,,https://doi.org/10.1007/978-3-319-03734-9
  36. Takeaki Iwamoto, Shintaro Ishida. Multiple Bonds with Silicon: Recent Advances in Synthesis, Structure, and Functions of Stable Disilenes. 2013,,, 125-202. https://doi.org/10.1007/430_2013_119
  37. . Functional Molecular Silicon Compounds II. 2014,,https://doi.org/10.1007/978-3-319-03734-9
  38. V.Ya. Lee, A. Sekiguchi. Multiply Bonded Compounds of Group 14 Elements. 2013,,, 289-324. https://doi.org/10.1016/B978-0-08-097774-4.00113-3
  39. . Comprehensive Inorganic Chemistry II. 2013,,https://doi.org/
  40. Xu-Qiong Xiao, Hui Zhao, Jun Luo, Zheng Xu, Guo-Qiao Lai, Zhifang Li. Synthesis and characterization of heterocyclic disilylchalcogenides. Dalton Transactions 2013, 42 (11) , 3994. https://doi.org/10.1039/c2dt32406g
  41. Ming-Der Su, Ling-Hsuan Liu. A mechanistic analysis of the tetrasilyl-substituted trimetallaallenes, >EEE< (E = C, Si, Ge, Sn, and Pb). Dalton Transactions 2013, 42 (14) , 4873. https://doi.org/10.1039/c2dt32917d
  42. Ricardo Rodriguez, Thibault Troadec, Tsuyoshi Kato, Nathalie Saffon-Merceron, Jean-Marc Sotiropoulos, Antoine Baceiredo. Synthesis and Characterization of an Isolable Base-Stabilized Silacycloprop-1-ylidene. Angewandte Chemie 2012, 124 (29) , 7270-7273. https://doi.org/10.1002/ange.201201581
  43. Ricardo Rodriguez, Thibault Troadec, Tsuyoshi Kato, Nathalie Saffon-Merceron, Jean-Marc Sotiropoulos, Antoine Baceiredo. Synthesis and Characterization of an Isolable Base-Stabilized Silacycloprop-1-ylidene. Angewandte Chemie International Edition 2012, 51 (29) , 7158-7161. https://doi.org/10.1002/anie.201201581
  44. Sakya S. Sen, Shabana Khan, Prinson P. Samuel, Herbert W. Roesky. Chemistry of functionalized silylenes. Chem. Sci. 2012, 3 (3) , 659-682. https://doi.org/10.1039/C1SC00757B
  45. Jonathan Parr. Carbon, silicon, germanium, tin and lead. Annual Reports Section "A" (Inorganic Chemistry) 2012, 108 , 85. https://doi.org/10.1039/c2ic90021a
  46. Ricardo Rodriguez, David Gau, Yohan Contie, Tsuyoshi Kato, Nathalie Saffon-Merceron, Antoine Baceiredo. Synthesis of a Phosphine-Stabilized Silicon(II) Hydride and Its Addition to Olefins: A Catalyst-Free Hydrosilylation Reaction. Angewandte Chemie 2011, 123 (48) , 11694-11697. https://doi.org/10.1002/ange.201105639
  47. Ricardo Rodriguez, David Gau, Yohan Contie, Tsuyoshi Kato, Nathalie Saffon-Merceron, Antoine Baceiredo. Synthesis of a Phosphine-Stabilized Silicon(II) Hydride and Its Addition to Olefins: A Catalyst-Free Hydrosilylation Reaction. Angewandte Chemie International Edition 2011, 50 (48) , 11492-11495. https://doi.org/10.1002/anie.201105639
  48. . Chemie. Nachrichten aus der Chemie 2011,,, 810-813. https://doi.org/10.1002/nadc.201190010

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

OOPS

You have to login with your ACS ID befor you can login with your Mendeley account.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE