An Electrochemical Strategy to Synthesize Disilanes and Oligosilanes from Chlorosilanes**

Guan, Weiyang; Lu, Lingxiang; Jiang, Qifeng; Gittens, Alexandra F.; Wang, Yi; Novaes, Luiz F. T.; Klausen, Rebekka S.; Lin, Song

doi:10.1002/anie.202303592

An Electrochemical Strategy to Synthesize Disilanes and Oligosilanes from Chlorosilanes**

Journal Article · Fri Apr 21 00:00:00 EDT 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202303592· OSTI ID:2329218

^[1]; ^[2]; ^[3]; ^[3]; Wang, Yi ^[2]; Novaes, Luiz F. T. ^[2]; ^[3]; ^[2]

Cornell University, Ithaca, NY (United States); Johns Hopkins University
Cornell University, Ithaca, NY (United States)
Johns Hopkins University, Baltimore, MD (United States)

Silanes are important compounds in industrial and synthetic chemistry. Here, we develop a general approach for the synthesis of disilanes as well as linear and cyclic oligosilanes via the reductive activation of readily available chlorosilanes. The efficient and selective generation of silyl anion intermediates, which are arduous to achieve by other means, allows for the synthesis of various novel oligosilanes by heterocoupling. In particular, this work presents a modular synthesis for a variety of functionalized cyclosilanes, which may give rise to materials with distinct properties from linear silanes but remain challenging synthetic targets. In comparison to the traditional Wurtz coupling, our method features milder conditions and improved chemoselectivity, broadening the functional groups that are compatible in oligosilane preparation. Furthermore, computational studies support a mechanism whereby differential activation of sterically and electronically distinct chlorosilanes are achieved in an electrochemically driven radical-polar crossover mechanism.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins University, Baltimore, MD (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020681

OSTI ID:: 2329218

Alternate ID(s):: OSTI ID: 1973873

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 26 Vol. 62; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (74)

Simple Synthesis of Oligosilyl-α,ω-dipotassium Compounds Kayser, Christian; Kickelbick, Guido; Marschner, Christoph Angewandte Chemie International Edition, Vol. 41, Issue 6 https://doi.org/10.1002/1521-3773(20020315)41:6<989::AID-ANIE989>3.0.CO;2-A	journal	March 2002
A New Electrochemical Method of Forming SiSi Bonds Hengge, Edwin; Litscher, Georg Angewandte Chemie International Edition in English, Vol. 15, Issue 6 https://doi.org/10.1002/anie.197603701	journal	June 1976
Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane) Press, Eric M.; Marro, Eric A.; Surampudi, Sravan K. Angewandte Chemie International Edition, Vol. 56, Issue 2 https://doi.org/10.1002/anie.201610208	journal	November 2016
Active Molybdenum-Based Anode for Dehydrogenative Coupling Reactions Beil, Sebastian B.; Müller, Timo; Sillart, Sydney B. Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201712718	journal	February 2018
Enantioselective Intermolecular C−H Silylation of Heteroarenes for the Synthesis of Acyclic Si‐Stereogenic Silanes Chen, Shuyou; Zhu, Jiefeng; Ke, Jie Angewandte Chemie International Edition, Vol. 61, Issue 21 https://doi.org/10.1002/anie.202117820	journal	March 2022
Recent Progress in the Transition‐Metal‐Catalyzed Activation of Si−Si Bonds To Form C−Si Bonds Xiao, Peihong; Gao, Lu; Song, Zhenlei Chemistry – A European Journal, Vol. 25, Issue 10 https://doi.org/10.1002/chem.201803803	journal	December 2018
Hydrogen‐Bridged Oligosilanylsilyl Mono‐ and Oligosilanylsilyl Dications Nimoth, Jelte P.; Müller, Thomas Chemistry – A European Journal, Vol. 28, Issue 9 https://doi.org/10.1002/chem.202104318	journal	December 2021
Synthesis of Alkoxy‐Substituted Oligosilanes using [ β ‐(Alkoxy)disilanyl]lithium Matsuo, Takumi; Yamaguchi, Tatsuya; Hirohata, Tomoki European Journal of Inorganic Chemistry, Vol. 2021, Issue 39 https://doi.org/10.1002/ejic.202100668	journal	September 2021
Isolation of a Cyclopentasilane from Magnesium Reduction of a Linear Hexasilane Ballestero‐Martínez, Ernesto; Ferguson, John T.; Siegler, Maxime A. European Journal of Organic Chemistry, Vol. 2021, Issue 33 https://doi.org/10.1002/ejoc.202100768	journal	September 2021
Photoinduced Reductive Coupling of Organochlorosilanes with SmI₂/Sm Yoshimura, Aya; Tomisaka, Yuri; Li, Zhifang Heteroatom Chemistry, Vol. 25, Issue 6 https://doi.org/10.1002/hc.21186	journal	July 2014
XEDA , a fast and multipurpose energy decomposition analysis program Tang, Zhen; Song, Yanlin; Zhang, Shu Journal of Computational Chemistry, Vol. 42, Issue 32 https://doi.org/10.1002/jcc.26765	journal	October 2021
General atomic and molecular electronic structure system Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A. Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363 https://doi.org/10.1002/jcc.540141112	journal	November 1993
Generalized Kohn‐Sham energy decomposition analysis and its applications Su, Peifeng; Tang, Zhen; Wu, Wei WIREs Computational Molecular Science, Vol. 10, Issue 5 https://doi.org/10.1002/wcms.1460	journal	January 2020
Synthese und Deprotonierung des verzweigten Triphosphanyltetrasilans PhSi(SiMe₂PH₂)₃ von Hänisch, Carsten; Feierabend, Michael Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 5 https://doi.org/10.1002/zaac.201200544	journal	March 2013
New ways to polysilanes Hengge, Edwin F. Journal of Inorganic and Organometallic Polymers, Vol. 3, Issue 4 https://doi.org/10.1007/BF00683955	journal	December 1993
Photolysis of organopolysilanes. Synthesis and photochemical behavior of Si-silyl substituted polysilacycloalkanes Ishikawa, Mitsuo; Yamanaka, Toru; Kumada, Makoto Journal of Organometallic Chemistry, Vol. 292, Issue 1-2 https://doi.org/10.1016/0022-328X(85)87332-0	journal	September 1985
Synthesis, properties and characterization of octadecamethylbicyclo[4.4.O]decasilane Jenkner, Peter K.; Hengge, Edwin; Czaputa, Rainer Journal of Organometallic Chemistry, Vol. 446, Issue 1-2 https://doi.org/10.1016/0022-328X(93)80038-D	journal	March 1993
Electroreductive synthesis of oligosilanes and polysilanes with ordered sequences Ishifune, Manabu; Kashimura, Shigenori; Kogai, Yasumichi Journal of Organometallic Chemistry, Vol. 611, Issue 1-2 https://doi.org/10.1016/S0022-328X(00)00327-2	journal	October 2000
An electrochemical method for the synthesis of silicon—silicon bonds Hengge, E.; Firgoi, H. Journal of Organometallic Chemistry, Vol. 212, Issue 2 https://doi.org/10.1016/S0022-328X(00)81911-7	journal	June 1981
Electrochemical reduction of triorganohalo-silanes and -germanes Corriu, R. J. P.; Dabosi, G.; Martineau, M. Journal of Organometallic Chemistry, Vol. 188, Issue 1 https://doi.org/10.1016/S0022-328X(00)83697-9	journal	April 1980
Synthesis and properties of substituted methylcyclopolysilanes J. Helmer, Bradley; West, Robert Journal of Organometallic Chemistry, Vol. 236, Issue 1 https://doi.org/10.1016/S0022-328X(00)86746-7	journal	September 1982
Electrochemical reduction of alkoxychlorosilanes for Si–Si bond formation Ohshita, Joji; Hino, Koichi; Iwawaki, Tomonori Journal of Electroanalytical Chemistry, Vol. 625, Issue 2 https://doi.org/10.1016/j.jelechem.2008.10.022	journal	January 2009
Route Si6 revisited Fischer, Roland; Konopa, Tina; Ully, Stephan Journal of Organometallic Chemistry, Vol. 685, Issue 1-2 https://doi.org/10.1016/j.jorganchem.2003.02.002	journal	November 2003
Electrochemical synthesis of symmetrical difunctional disilanes as precursors for organofunctional silanes Grogger, Christa; Loidl, Bernhard; Stueger, Harald Journal of Organometallic Chemistry, Vol. 691, Issue 1-2 https://doi.org/10.1016/j.jorganchem.2005.08.016	journal	January 2006
Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides Varaprath, Sudarsanan; Stutts, Debra H. Journal of Organometallic Chemistry, Vol. 692, Issue 10 https://doi.org/10.1016/j.jorganchem.2006.12.032	journal	April 2007
Scope and selectivity of B(C6F5)3-catalyzed reactions of the disilane (Ph2SiH)2 Lee, Peter T. K.; Rosenberg, Lisa Journal of Organometallic Chemistry, Vol. 809 https://doi.org/10.1016/j.jorganchem.2016.02.035	journal	May 2016
Ruthenium-catalyzed hydrosilylation of alkynes by using hydrooligosilanes without Si–Si bond cleavage Kanno, Ken-ichiro; Aikawa, Yumi; Kyushin, Soichiro Tetrahedron Letters, Vol. 61, Issue 36 https://doi.org/10.1016/j.tetlet.2020.152274	journal	September 2020
Comparison of the Conductivity Properties of the Tetrabutylammonium Salt of Tetrakis(pentafluorophenyl)borate Anion with Those of Traditional Supporting Electrolyte Anions in Nonaqueous Solvents LeSuer, Robert J.; Buttolph, Catherine; Geiger, William E. Analytical Chemistry, Vol. 76, Issue 21 https://doi.org/10.1021/ac040087x	journal	November 2004
Conjugated Polymers Inspired by Crystalline Silicon Marro, Eric A.; Klausen, Rebekka S. Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.9b00131	journal	March 2019
Conjugation in Isomeric Cyclosilane Thioethers Gittens, Alexandra F.; Jiang, Qifeng; Siegler, Maxime A. Organometallics, Vol. 41, Issue 23 https://doi.org/10.1021/acs.organomet.2c00501	journal	November 2022
Low-Energy Electronic Transition in SiB Rings Purkait, Tapas K.; Press, Eric M.; Marro, Eric A. Organometallics, Vol. 38, Issue 8 https://doi.org/10.1021/acs.organomet.8b00804	journal	December 2018
Homocyclic Silanes Hengge, Edwin.; Janoschek, Rudolf. Chemical Reviews, Vol. 95, Issue 5 https://doi.org/10.1021/cr00037a016	journal	July 1995
Polysilane high polymers Miller, Robert D.; Michl, Josef Chemical Reviews, Vol. 89, Issue 6 https://doi.org/10.1021/cr00096a006	journal	September 1989
Catalytic Silylation of Unactivated C–H Bonds Cheng, Chen; Hartwig, John F. Chemical Reviews, Vol. 115, Issue 17 https://doi.org/10.1021/cr5006414	journal	February 2015
Catalytic Dehydrogenative Coupling of Secondary Silanes Using Wilkinson's Catalyst Rosenberg, Lisa; Davis, Colin W.; Yao, Junzhi Journal of the American Chemical Society, Vol. 123, Issue 21 https://doi.org/10.1021/ja015697i	journal	May 2001
Conductive Molecular Silicon Klausen, Rebekka S.; Widawsky, Jonathan R.; Steigerwald, Michael L. Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja211677q	journal	March 2012
Optical Properties of Disilane-Bridged Donor–Acceptor Architectures: Strong Effect of Substituents on Fluorescence and Nonlinear Optical Properties Shimada, Masaki; Yamanoi, Yoshinori; Matsushita, Tomonori Journal of the American Chemical Society, Vol. 137, Issue 3 https://doi.org/10.1021/ja511177e	journal	January 2015
General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis Shishido, Ryosuke; Uesugi, Minami; Takahashi, Rikuro Journal of the American Chemical Society, Vol. 142, Issue 33 https://doi.org/10.1021/jacs.0c03011	journal	July 2020
Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism Zhang, Wen; Lin, Song Journal of the American Chemical Society, Vol. 142, Issue 49 https://doi.org/10.1021/jacs.0c08532	journal	November 2020
An Electroreductive Approach to Radical Silylation via the Activation of Strong Si–Cl Bond Lu, Lingxiang; Siu, Juno C.; Lai, Yihuan Journal of the American Chemical Society, Vol. 142, Issue 51 https://doi.org/10.1021/jacs.0c10899	journal	December 2020
Poly(cyclosilane) Connectivity Tunes Optical Absorbance Fang, Fan; Jiang, Qifeng; Klausen, Rebekka S. Journal of the American Chemical Society, Vol. 144, Issue 17 https://doi.org/10.1021/jacs.2c01820	journal	April 2022
Decasilahexahydrotriquinacene and Decasilaisotwistane: σ Conjugation on a Bowl Surface Tsurusaki, Akihiro; Koyama, Yu; Kyushin, Soichiro Journal of the American Chemical Society, Vol. 139, Issue 11 https://doi.org/10.1021/jacs.7b00250	journal	February 2017
Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence Shimada, Masaki; Yamanoi, Yoshinori; Ohto, Tatsuhiko Journal of the American Chemical Society, Vol. 139, Issue 32 https://doi.org/10.1021/jacs.7b05671	journal	August 2017
Directional Building Blocks Determine Linear and Cyclic Silicon Architectures Marro, Eric A.; Press, Eric M.; Siegler, Maxime A. Journal of the American Chemical Society, Vol. 140, Issue 18 https://doi.org/10.1021/jacs.8b02541	journal	April 2018
Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes Li, Haixing; Garner, Marc H.; Shangguan, Zhichun Journal of the American Chemical Society, Vol. 140, Issue 44 https://doi.org/10.1021/jacs.8b10296	journal	October 2018
Stereocontrolled Syntheses of Functionalized cis - and trans -Siladecalins Marro, Eric A.; Folster, Carlton P.; Press, Eric M. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b09902	journal	October 2019
Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes¹ Kashimura, Shigenori; Ishifune, Manabu; Yamashita, Natsuki The Journal of Organic Chemistry, Vol. 64, Issue 18 https://doi.org/10.1021/jo990180z	journal	August 1999
Energy Decomposition Scheme Based on the Generalized Kohn–Sham Scheme Su, Peifeng; Jiang, Zhen; Chen, Zuochang The Journal of Physical Chemistry A, Vol. 118, Issue 13 https://doi.org/10.1021/jp500405s	journal	March 2014
Tuning of the Luminescence in Multiblock Alternating Copolymers. 1. Synthesis and Spectroscopy of Poly[(silanylene)thiophene]s Herrema, Jan K.; Wildeman, Jurjen; Gill, Richard E. Macromolecules, Vol. 28, Issue 24 https://doi.org/10.1021/ma00128a020	journal	November 1995
Catalytic Hydrosilylation Routes to Divinylbenzene Bridged Silole and Silafluorene Polymers. Applications to Surface Imaging of Explosive Particulates Sanchez, Jason C.; Urbas, Sara A.; Toal, Sarah J. Macromolecules, Vol. 41, Issue 4 https://doi.org/10.1021/ma702274c	journal	February 2008
Synthesis and Polymerization of an Optically Active Bifunctional Disiloxane. 1. Preparation of Optically Active and Highly Stereoregular Poly[{(1S)-1-(1-naphthyl)-1-phenyl-3,3-dimethyldisiloxane-1,3-diyl}ethylene] by Polyaddition via Hydrosilylation Li, Yuning; Kawakami, Yusuke Macromolecules, Vol. 31, Issue 17 https://doi.org/10.1021/ma980463d	journal	August 1998
Mechanism of pyrolysis of polycarbosilanes: poly(silylethylene) and poly(dimethylsilylethylene) Corriu, Robert J. P.; Leclercq, Dominique; Mutin, P. Hubert Organometallics, Vol. 12, Issue 2 https://doi.org/10.1021/om00026a032	journal	February 1993
Electrochemistry of organosilicon compounds. 1. Synthesis of di- and trisilanes with use of mercury and silver electrode systems Kunai, Atsutaka; Kawakami, Toshihiro; Toyoda, Eiji Organometallics, Vol. 10, Issue 4 https://doi.org/10.1021/om00050a018	journal	April 1991
Catalytic dehydrogenative coupling of secondary silanes with Cp2MCl2-BuLi Corey, Joyce Y.; Zhu, Xiao Hong.; Bedard, Thomas C. Organometallics, Vol. 10, Issue 4 https://doi.org/10.1021/om00050a024	journal	April 1991
A new class of silicon compounds with interesting nonlinear optical effects Mignani, Gerard; Kramer, A.; Puccetti, G. Organometallics, Vol. 9, Issue 10 https://doi.org/10.1021/om00160a004	journal	October 1990
Preparation and Reactions of Polysilanyl Anions and Dianions Marschner, Christoph Organometallics, Vol. 25, Issue 9 https://doi.org/10.1021/om0509793	journal	March 2006
New Entry to the Construction of Si−Si Linkages: Sm/SmI ₂ -Induced Efficient Reductive Coupling of Organochlorosilanes Li, Zhifang; Iida, Koichiro; Tomisaka, Yuri Organometallics, Vol. 26, Issue 5 https://doi.org/10.1021/om060745z	journal	February 2007
Borane-Catalyzed Si–H Activation Routes to Polysilanes Containing Thiolato Side Chains Lee, Peter T. K.; Skjel, Miranda K.; Rosenberg, Lisa Organometallics, Vol. 32, Issue 6 https://doi.org/10.1021/om301246z	journal	February 2013
Stepwise on-demand functionalization of multihydrosilanes enabled by a hydrogen-atom-transfer photocatalyst based on eosin Y Fan, Xuanzi; Zhang, Muliang; Gao, Yuanjun Nature Chemistry, Vol. 15, Issue 5 https://doi.org/10.1038/s41557-023-01155-8	journal	March 2023
Comprehensive suppression of single-molecule conductance using destructive σ-interference Garner, Marc H.; Li, Haixing; Chen, Yan Nature, Vol. 558, Issue 7710 https://doi.org/10.1038/s41586-018-0197-9	journal	June 2018
Electrochemically driven cross-electrophile coupling of alkyl halides Zhang, Wen; Lu, Lingxiang; Zhang, Wendy Nature, Vol. 604, Issue 7905 https://doi.org/10.1038/s41586-022-04540-4	journal	February 2022
Increased carrier mobility in end-functionalized oligosilanes Surampudi, S.; Yeh, M. -L.; Siegler, M. A. Chemical Science, Vol. 6, Issue 3 https://doi.org/10.1039/C4SC03274H	journal	January 2015
Conformations of cyclopentasilane stereoisomers control molecular junction conductance Li, Haixing; Garner, Marc H.; Shangguan, Zhichun Chemical Science, Vol. 7, Issue 9 https://doi.org/10.1039/C6SC01360K	journal	January 2016
About the selectivity and reactivity of active nickel electrodes in C–C coupling reactions Beil, Sebastian B.; Breiner, Manuel; Schulz, Lara RSC Advances, Vol. 10, Issue 24 https://doi.org/10.1039/D0RA02673E	journal	January 2020
Highly selective addition of cyclosilanes to alkynes enabling new conjugated materials Jiang, Qifeng; Gittens, Alexandra F.; Wong, Sydnee Chemical Science, Vol. 13, Issue 25 https://doi.org/10.1039/D2SC01690G	journal	January 2022
Toward selective functionalisation of oligosilanes: borane-catalysed dehydrogenative coupling of silanes with thiols Harrison, Daniel J.; Edwards, David R.; McDonald, Robert Dalton Transactions, Issue 26 https://doi.org/10.1039/b806270f	journal	January 2008
Reversed redox generation of silyl radicals in a four-electrode flow-through EPR spectroelectrochemical cell Zeitouny, Joceline; Jouikov, Viatcheslav Physical Chemistry Chemical Physics, Vol. 11, Issue 33 https://doi.org/10.1039/b905072h	journal	January 2009
Electroreductive formation of polysilanes Shono, Tatsuya; Kashimura, Shigenori; Ishifune, Manabu Journal of the Chemical Society, Chemical Communications, Issue 17 https://doi.org/10.1039/c39900001160	journal	January 1990
Synthesis and Structure of Sila-Adamantane Fischer, Jelena; Baumgartner, Judith; Marschner, Christoph Science, Vol. 310, Issue 5749 https://doi.org/10.1126/science.1118981	journal	November 2005
Permethylpolysilanes: Silicon Analogs of Hydrocarbons West, Robert; Carberry, Edward Science, Vol. 189, Issue 4198 https://doi.org/10.1126/science.189.4198.179	journal	July 1975
Synthesis, ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance spectra and crystal structure of trans-1,4-diphenyldecamethylcyclohexasilane Kumar, Kanta; Litt, Morton H.; Chadha, Raj K. Canadian Journal of Chemistry, Vol. 65, Issue 2 https://doi.org/10.1139/v87-074	journal	February 1987
Continuous Silicon Carbide Fiber of high Tensile Strength Yajima, Seishi; Hayashi, Josaburo; Omori, Mamoru Chemistry Letters, Vol. 4, Issue 9 https://doi.org/10.1246/cl.1975.931	journal	September 1975
Octamethyltetrasila[2.2]paracyclophane. Cyclophanes Bridged by Polysilanes Sakurai, Hideki; Hoshi, Satoshi; Kamiya, Akihiko Chemistry Letters, Vol. 15, Issue 10 https://doi.org/10.1246/cl.1986.1781	journal	October 1986
Electron delocalization and "aromatic" behavior in cyclic polysilanes West, R. Pure and Applied Chemistry, Vol. 54, Issue 5 https://doi.org/10.1351/pac198254051041	journal	January 1982

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