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A New Disilene with π-Accepting Groups from the Reaction of Disilyne RSi≡SiR (R = SiiPr[CH(SiMe3)2]) with Isocyanides

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
[email protected]
Cite this: J. Am. Chem. Soc. 2012, 134, 6, 2954–2957
Publication Date (Web):January 26, 2012
https://doi.org/10.1021/ja212065a
Copyright © 2012 American Chemical Society
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Abstract

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The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne (1) with tert-butylisocyanide or tert-octylisocyanide produced the corresponding disilyne–isocyanide adducts [RSiSiR(CNR′)2] (R = SiiPr[CH(SiMe3)2]2, R′ = tBu (2a) or CMe2CH2tBu (2b)), which are stable below −30 °C and were characterized by spectroscopic data and, in the case of 2a, X-ray crystallography. Upon warming to room temperature, 2 underwent thermal decomposition to produce 1,2-dicyanodisilene R(NC)Si═Si(CN)R (3) and 1,2-dicyanodisilane R(NC)HSiSiH(CN)R (4) via C–N bond cleavage and elimination of an alkane and an alkene. The 1,2-dicyanodisilene derivative 3 was characterized by X-ray crystallography.

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Experimental procedures for 2a, 2b, and 3; computational results on model compounds 3′ and 3″; calculated BDEs of 2a, 2c, Me2N–CMe3, Me2N–SiMe3, and model compound 2d; and crystallographic data including atomic positional and thermal parameters for 2a and 3 (PDF/CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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  7. Annette D. Allen and Thomas T. Tidwell . Ketenes and Other Cumulenes as Reactive Intermediates. Chemical Reviews 2013, 113 (9) , 7287-7342. https://doi.org/10.1021/cr3005263
  8. Zachary D. Brown and Philip P. Power . Mechanisms of Reactions of Open-Shell, Heavier Group 14 Derivatives with Small Molecules: n−π* Back-Bonding in Isocyanide Complexes, C–H Activation under Ambient Conditions, CO Coupling, and Ancillary Molecular Interactions†This Award Article summarizes, including more recent results, one of the themes of a lecture presented on March 26th, 2012, at the 243rd Chemical Society National Meeting American in San Diego, CA, in receipt of the 2012 Award in Organometallic Chemistry sponsored by the Dow Corporation.. Inorganic Chemistry 2013, 52 (11) , 6248-6259. https://doi.org/10.1021/ic4007058
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  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. Frank Uhlig. 29 Si NMR Spectroscopy. 2017,,, 59-77. https://doi.org/10.1016/B978-0-12-814213-4.00002-2
  18. . Organosilicon Compounds. 2017,,https://doi.org/
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  22. Wataru Taniwaki, Shun Ohta, Masaaki Okazaki. Activation of Isocyanides and Hydrosilanes by a Cationic [CCH] Subunit in a Tetrairon–Tetracarbon Cluster. Bulletin of the Chemical Society of Japan 2016, 89 (1) , 11-19. https://doi.org/10.1246/bcsj.20150289
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  24. Julian Böhnke, Holger Braunschweig, Theresa Dellermann, William C. Ewing, Thomas Kramer, Ivo Krummenacher, Alfredo Vargas. Von einem elektronenreichen Bis(boraketenimin) zu einem elektronenarmen Diboren. Angewandte Chemie 2015, 127 (15) , 4551-4555. https://doi.org/10.1002/ange.201412006
  25. Julian Böhnke, Holger Braunschweig, Theresa Dellermann, William C. Ewing, Thomas Kramer, Ivo Krummenacher, Alfredo Vargas. From an Electron-Rich Bis(boraketenimine) to an Electron-Poor Diborene. Angewandte Chemie International Edition 2015, 54 (15) , 4469-4473. https://doi.org/10.1002/anie.201412006
  26. Julie A. Hardwick, Kim M. Baines. The Addition of Nitriles to Tetramesityldisilene: A Comparison of the Reactivity between Surface and Molecular Disilenes. Chemistry - A European Journal 2015, 21 (6) , 2480-2488. https://doi.org/10.1002/chem.201405780
  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
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  29. Moumita Majumdar, Volker Huch, Iulia Bejan, Antje Meltzer, David Scheschkewitz. Reversible, Complete Cleavage of SiSi Double Bonds by Isocyanide Insertion. Angewandte Chemie International Edition 2013, 52 (12) , 3516-3520. https://doi.org/10.1002/anie.201209281
  30. Roland C. Fischer, Jan J. Weigand. Anorganische Chemie 2012. Nachrichten aus der Chemie 2013, 61 (3) , 219-234. https://doi.org/10.1002/nadc.201390083
  31. 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
  32. . Functional Molecular Silicon Compounds II. 2014,,https://doi.org/10.1007/978-3-319-03734-9
  33. Jonathan Parr. Carbon, silicon, germanium, tin and lead. Annual Reports Section "A" (Inorganic Chemistry) 2013, 109 , 53. https://doi.org/10.1039/c3ic90019c
  34. Matthew Asay, Akira Sekiguchi. Recent Developments in the Reactivity of Stable Disilynes. Bulletin of the Chemical Society of Japan 2012, 85 (12) , 1245-1261. https://doi.org/10.1246/bcsj.20120212

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