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The First Silastannene >SiSn<:  A New Doubly-Bonded System of Heavier Group 14 Elements

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Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2002, 124, 50, 14822–14823
Publication Date (Web):November 20, 2002
https://doi.org/10.1021/ja021077l
Copyright © 2002 American Chemical Society
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Abstract

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The reaction of bis[di-tert-butyl(methyl)silyl]dilithiosilane 1 with dichlorobis(2,4,6-triisopropylphenyl)stannane in THF at room temperature yielded highly air- and moisture-sensitive deep violet crystals of 1,1-bis[di-tert-butyl(methyl)silyl]-2,2-bis(2,4,6-triisopropylphenyl)-1-sila-2-stannaethene 2 with a SiSn double bond. The molecular structure of 2 was established by X-ray crystallography, which showed a trans-bent structure (bending angles of 26.2° for the sp2 Si atom and 9.6° for the sp2 Sn atom) with a >SiSn< bond length of 2.4188(14) Å and a twisting angle of 34.6°. The geometry and regioselectivity of the addition reaction of PhEH (E = O and S) corresponds to the polarity of the double bond Siδ-Snδ+, which is also supported by theoretical calculations on the model silastannene (H3Si)2SiSnPh2.

*

 To whom correspondence should be addressed. E-mail:  sek[email protected] staff.chem.tsukuba.ac.jp.

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Experimental procedures and spectral data of 3 and 4, tables of crystallographic data including atomic positional and thermal parameters for 2 (PDF/CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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  2. Henning Arp, Christoph Marschner, Judith Baumgartner, Patrick Zark, and Thomas Müller . Coordination Chemistry of Disilylated Stannylenes with Group 10 d10 Transition Metals: Silastannene vs Stannylene Complexation. Journal of the American Chemical Society 2013, 135 (21) , 7949-7959. https://doi.org/10.1021/ja401548d
  3. Vladimir Ya. Lee and Akira Sekiguchi . Novel Organometallic Reagents: Geminal Dianionic Derivatives of the Heavy Group 14 Elements. Inorganic Chemistry 2011, 50 (24) , 12303-12314. https://doi.org/10.1021/ic2006106
  4. Roland C. Fischer and Philip P. Power . π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium. Chemical Reviews 2010, 110 (7) , 3877-3923. https://doi.org/10.1021/cr100133q
  5. Stefan Spirk, Ferdinand Belaj, Jörg H. Albering and Rudolf Pietschnig . Formation of a Silylated 1-Silaallene via an Intermediate 1-Chloro-1-silaallene. Organometallics 2010, 29 (13) , 2981-2986. https://doi.org/10.1021/om100299w
  6. Johann Hlina, Christian Mechtler, Harald Wagner, Judith Baumgartner and Christoph Marschner. Multiple Silyl Exchange Reactions: A Way to Spirooligosilanes. Organometallics 2009, 28 (14) , 4065-4071. https://doi.org/10.1021/om900287c
  7. Young Mook Lim, Myong Euy Lee, Junseong Lee and Youngkyu Do . Reactivity of Bromodilithiosilane to Naphthalene and Anthracene. Organometallics 2008, 27 (23) , 6375-6378. https://doi.org/10.1021/om800596t
  8. Masayasu Igarashi,, Masaaki Ichinohe, and, Akira Sekiguchi. Air-Stable Disilacyclopropene with a SiC Bond and Its Conversion to Disilacyclopropenylium Ion:  Silicon−Carbon Hybrid 2π-Electron Systems. Journal of the American Chemical Society 2007, 129 (42) , 12660-12661. https://doi.org/10.1021/ja075740n
  9. Masaaki Ichinohe,, Masayasu Igarashi,, Kaori Sanuki, and, Akira Sekiguchi. Cyclotrisilenylium Ion:  The Persilaaromatic Compound. Journal of the American Chemical Society 2005, 127 (28) , 9978-9979. https://doi.org/10.1021/ja053202+
  10. Yuki Kuramoto,, Noriyuki Sawai,, Yusuke Fujiwara,, Michinori Sumimoto,, Yoshihide Nakao,, Hirofumi Sato, and, Shigeyoshi Sakaki. Stabilization of Vinylidene-type and Acetylene-type Si2H2 Species by Coordination with Rhodium(I) and Platinum(0) Complexes. Theoretical Proposals. Organometallics 2005, 24 (15) , 3655-3663. https://doi.org/10.1021/om050337f
  11. Masaichi Saito,, Norihiro Tokitoh, and, Renji Okazaki. Tin−Chalcogen Double-Bond Compounds, Stannanethione and Stannaneselone:  Synthesis, Structure, and Reactivities. Journal of the American Chemical Society 2004, 126 (47) , 15572-15582. https://doi.org/10.1021/ja048453h
  12. Akira Sekiguchi,, Shigeyoshi Inoue,, Masaaki Ichinohe, and, Yoriko Arai. Isolable Anion Radical of Blue Disilene (tBu2MeSi)2SiSi(SiMetBu2)2 Formed upon One-Electron Reduction:  Synthesis and Characterization. Journal of the American Chemical Society 2004, 126 (31) , 9626-9629. https://doi.org/10.1021/ja040079y
  13. Vladimir Ya. Lee and, Akira Sekiguchi. Heteronuclear Heavy Alkenes EE‘ (E, E‘ = Group 14 Elements):  Germasilenes, Silastannenes, Germastannenes...Next Stop?. Organometallics 2004, 23 (12) , 2822-2834. https://doi.org/10.1021/om040027h
  14. Masaaki Ichinohe,, Kaori Sanuki,, Shigeyoshi Inoue, and, Akira Sekiguchi. Disilenyllithium from Tetrasila-1,3-butadiene:  A Silicon Analogue of a Vinyllithium. Organometallics 2004, 23 (13) , 3088-3090. https://doi.org/10.1021/om040056s
  15. Norio Nakata,, Rika Izumi,, Vladimir Ya. Lee,, Masaaki Ichinohe, and, Akira Sekiguchi. 1,3-Disila-2-gallata- and -indataallenic Anions [>SiMSi<]-·Li+ (M = Ga, In):  Compounds Featuring Double Bonds between Elements of Groups 13 and 14. Journal of the American Chemical Society 2004, 126 (16) , 5058-5059. https://doi.org/10.1021/ja040001h
  16. Masaaki Ichinohe,, Rei Kinjo, and, Akira Sekiguchi. The First Stable Methyl-Substituted Disilene:  Synthesis, Crystal Structure, and Regiospecific MeLi Addition. Organometallics 2003, 22 (23) , 4621-4623. https://doi.org/10.1021/om030571a
  17. Manfred Weidenbruch. From a Cyclotrisilane to a Cyclotriplumbane:  Low Coordination and Multiple Bonding in Group 14 Chemistry. Organometallics 2003, 22 (22) , 4348-4360. https://doi.org/10.1021/om034085z
  18. Akira Sekiguchi,, Rika Izumi,, Vladimir Ya. Lee, and, Masaaki Ichinohe. R2GeSnR‘2 and RR‘GeSnRR‘ (R = SiMetBu2, R‘ = 2,4,6-iPr3C6H2):  The New Stable Germastannenes. Organometallics 2003, 22 (7) , 1483-1486. https://doi.org/10.1021/om021001y
  19. Catherine Weetman. Main Group Multiple Bonds for Bond Activations and Catalysis. Chemistry – A European Journal 2021, 27 (6) , 1941-1954. https://doi.org/10.1002/chem.202002939
  20. Abhishek Agarwal, Shubhankar Kumar Bose. Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14–16. Chemistry – An Asian Journal 2020, 15 (22) , 3784-3806. https://doi.org/10.1002/asia.202001043
  21. Masaichi Saito. Expansion of the Concept of Aromaticity by the Introduction of Heavy Atoms and Application to Coordination Chemistry. Journal of Synthetic Organic Chemistry, Japan 2019, 77 (10) , 960-970. https://doi.org/10.5059/yukigoseikyokaishi.77.960
  22. Christoph Marschner. Silicon-Centered Anions. 2017,,, 295-360. https://doi.org/10.1016/B978-0-12-801981-8.00007-1
  23. . Organosilicon Compounds. 2017,,https://doi.org/
  24. 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
  25. . Organosilicon Compounds. 2017,,https://doi.org/
  26. Debabrata Dhara, Thangavel Vijayakanth, Milan Kr. Barman, Khevath Praveen Kumar Naik, Nicolas Chrysochos, Cem B. Yildiz, Ramamoorthy Boomishankar, Carola Schulzke, Vadapalli Chandrasekhar, Anukul Jana. NHC-stabilized 1-hydrosilaimine: synthesis, structure and reactivity. Chemical Communications 2017, 53 (61) , 8592-8595. https://doi.org/10.1039/C7CC03912C
  27. Yu-Liang Shan, Bi-Xiang Leong, Hong-Wei Xi, Rakesh Ganguly, Yongxin Li, Kok Hwa Lim, Cheuk-Wai So. Reactivity of an amidinato silylene and germylene toward germanium( ii ), tin( ii ) and lead( ii ) halides. Dalton Transactions 2017, 46 (11) , 3642-3648. https://doi.org/10.1039/C7DT00051K
  28. Shintaro Ishida, Takeaki Iwamoto. Recent advances in η2-disilene and η2-disilyne mononuclear transition metal complexes and related compounds. Coordination Chemistry Reviews 2016, 314 , 34-63. https://doi.org/10.1016/j.ccr.2015.11.007
  29. Vladimir Ya. Lee, Akira Sekiguchi. 1,1-Dilithiosilanes, 1,1-dilithiogermanes, 1,1-dilithiostannanes and related compounds: Organometallic reagents of the new generation. Mendeleev Communications 2015, 25 (3) , 161-167. https://doi.org/10.1016/j.mencom.2015.05.001
  30. Yan Wang, Xiaolan Zeng. Theoretical study on the addition reactions of MeOH, PhOH and PhSH to silastannenes. Computational and Theoretical Chemistry 2015, 1058 , 12-20. https://doi.org/10.1016/j.comptc.2015.01.011
  31. 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
  32. . Comprehensive Inorganic Chemistry II. 2013,,https://doi.org/
  33. 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
  34. Takahiro Sasamori, Norihiro Tokitoh. Group 14 Multiple Bonding. 2011,,https://doi.org/10.1002/9781119951438.eibc0281
  35. . Encyclopedia of Inorganic and Bioinorganic Chemistry. 2011,,https://doi.org/
  36. S. M. Ibrahim Al-Rafia, Adam C. Malcolm, Robert McDonald, Michael J. Ferguson, Eric Rivard. Trapping the Parent Inorganic Ethylenes H2SiGeH2 and H2SiSnH2 in the Form of Stable Adducts at Ambient Temperature. Angewandte Chemie 2011, 123 (36) , 8504-8507. https://doi.org/10.1002/ange.201103576
  37. S. M. Ibrahim Al-Rafia, Adam C. Malcolm, Robert McDonald, Michael J. Ferguson, Eric Rivard. Trapping the Parent Inorganic Ethylenes H2SiGeH2 and H2SiSnH2 in the Form of Stable Adducts at Ambient Temperature. Angewandte Chemie International Edition 2011, 50 (36) , 8354-8357. https://doi.org/10.1002/anie.201103576
  38. . Heavy Analogs of Carbanions: Si-, Ge-, Sn- and Pb-Centered Anions. 2010,,, 89-138. https://doi.org/10.1002/9780470669266.ch3
  39. Vladimir Ya. Lee, Akira Sekiguchi. Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb. 2010,,https://doi.org/
  40. . Heavy Analogs of Alkenes, 1,3-Dienes, Allenes and Alkynes: Multiply Bonded Derivatives of Si, Ge, Sn and Pb. 2010,,, 199-334. https://doi.org/10.1002/9780470669266.ch5
  41. Vladimir Ya. Lee, Akira Sekiguchi. Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb. 2010,,https://doi.org/
  42. Vladimir Ya. Lee, Akira Sekiguchi, Jean Escudié, Henri Ranaivonjatovo. Heteronuclear Double Bonds E=E′ (E = Heavy Group 14 Element, E′ = Group 13–16 Element). Chemistry Letters 2010, 39 (4) , 312-318. https://doi.org/10.1246/cl.2010.312
  43. Andrea Ciccioli, Guido Gigli, Giovanni Meloni. The SiSn Chemical Bond: An Integrated Thermochemical and Quantum Mechanical Study of the SiSn Diatomic Molecule and Small SiâSn Clusters. Chemistry - A European Journal 2009, 15 (37) , 9543-9560. https://doi.org/10.1002/chem.200900804
  44. Norihiro Tokitoh, Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori. Synthesis and Characterization of the First Stable Stannanetelone. Phosphorus, Sulfur, and Silicon and the Related Elements 2008, 183 (4) , 948-955. https://doi.org/10.1080/10426500801900865
  45. H.C. Marsmann, F. Uhlig. 3 Chemical Shift. 2008,,, 12-46. https://doi.org/10.1007/978-3-540-45278-2_3
  46. , . Chemical Shifts and Coupling Constants for Silicon-29. 2008,,https://doi.org/10.1007/978-3-540-45278-2
  47. Tomoyuki Tajima, Takahiro Sasamori, Nobuhiro Takeda, Norihiro Tokitoh. Synthesis and Structure of a Kinetically Stabilized Stannanethione. Bulletin of the Chemical Society of Japan 2007, 80 (6) , 1202-1204. https://doi.org/10.1246/bcsj.80.1202
  48. Norio Nakata, Akira Sekiguchi. Thia- and Selenasilaboriranes and 1,3,2,4-Dioxasilaboretane from a Stable Silaborene. Chemistry Letters 2007, 36 (5) , 662-663. https://doi.org/10.1246/cl.2007.662
  49. Masaaki Ichinohe, Kaori Sanuki, Shigeyoshi Inoue, Akira Sekiguchi. Tetrasila-1,3-butadiene and its transformation to disilenyl anions. Silicon Chemistry 2007, 3 (3-4) , 111-116. https://doi.org/10.1007/s11201-006-9011-x
  50. J. Beckmann. Oligosilanes. 2007,,, 409-512. https://doi.org/10.1016/B0-08-045047-4/00050-9
  51. . Comprehensive Organometallic Chemistry III. 2007,,https://doi.org/
  52. A.G. Davies. Tin Organometallics. 2007,,, 809-883. https://doi.org/10.1016/B0-08-045047-4/00054-6
  53. . Comprehensive Organometallic Chemistry III. 2007,,https://doi.org/
  54. Dmitry Bravo-Zhivotovskii, Ilya Ruderfer, Semyon Melamed, Mark Botoshansky, Asher Schmidt, Yitzhak Apeloig. [{(tBu2Me)2Si}3Li4]2−: An Aggregated Dianion of a 1,1-Dilithiosilane with a Unique Structural Motif. Angewandte Chemie 2006, 118 (25) , 4263-4265. https://doi.org/10.1002/ange.200600308
  55. Dmitry Bravo-Zhivotovskii, Ilya Ruderfer, Semyon Melamed, Mark Botoshansky, Asher Schmidt, Yitzhak Apeloig. [{(tBu2Me)2Si}3Li4]2−: An Aggregated Dianion of a 1,1-Dilithiosilane with a Unique Structural Motif. Angewandte Chemie International Edition 2006, 45 (25) , 4157-4159. https://doi.org/10.1002/anie.200600308
  56. Matthias Driess, Stefan Block, Markus Brym, Michael T. Gamer. Synthese eines “halben” Phosphasilen-Stammsystems R2SiPH und seine Metallierung zumP-Zinkio-phosphasilen [R2SiPM]. Angewandte Chemie 2006, 118 (14) , 2351-2354. https://doi.org/10.1002/ange.200504145
  57. Matthias Driess, Stefan Block, Markus Brym, Michael T. Gamer. Synthesis of a “Half”-Parent Phosphasilene R2SiPH and Its Metalation to the CorrespondingP-Zinciophosphasilene [R2SiPM]. Angewandte Chemie International Edition 2006, 45 (14) , 2293-2296. https://doi.org/10.1002/anie.200504145
  58. Takahiro Sasamori, Norihiro Tokitoh. Group 14 Multiple Bonding. 2006,,https://doi.org/10.1002/0470862106.ia301
  59. , , , , . Encyclopedia of Inorganic Chemistry. 2006,,https://doi.org/
  60. Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori, Norihiro Tokitoh. Generation and Reactions of Overcrowded Diaryldilithiostannane and Diaryldipotassiostannane. European Journal of Inorganic Chemistry 2005, 2005 (21) , 4291-4300. https://doi.org/10.1002/ejic.200500375
  61. Roland Fischer, Frank Uhlig. Tin derivatives of organosilicon compounds. Coordination Chemistry Reviews 2005, 249 (19-20) , 2075-2093. https://doi.org/10.1016/j.ccr.2005.03.015
  62. Norio Nakata, Rika Izumi, Vladimir Ya. Lee, Masaaki Ichinohe, Akira Sekiguchi. Reaction of Dilithiosilane R 2 SiLi 2 and Dilithiogermane R 2 GeLi 2 (R = SiMe t Bu 2 ) with MesBCl 2 (Mes = 2,4,6-trimethylphenyl): Evidence for the Formation of Silaborene R 2 Si=BMes and Germaborene R 2 Ge=BMes. Chemistry Letters 2005, 34 (4) , 582-583. https://doi.org/10.1246/cl.2005.582
  63. Annette Beck-Sickinger, Holger Braunschweig, Matthias Epple, Barbara Kirchner, Markus Reiher, Joachim Spatz, Uta Wille, Annette Beck-Sickinger, Frederike Hammar, Claudia Schierloh, Anke Hübenthal. Notizen. Nachrichten aus der Chemie 2003, 51 (3) , 252-256. https://doi.org/10.1002/nadc.20030510305

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