Conjugation in Isomeric Cyclosilane Thioethers

Gittens, Alexandra F.; Jiang, Qifeng; Siegler, Maxime A.; Klausen, Rebekka Sidsel

doi:10.1021/acs.organomet.2c00501

Conjugation in Isomeric Cyclosilane Thioethers

Journal Article · Tue Nov 29 23:00:00 EST 2022 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.2c00501· OSTI ID:1900518

^[1]; Jiang, Qifeng ^[2]; ^[2]; ^[2]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
Johns Hopkins Univ., Baltimore, MD (United States)

Conjugation in thioether-functionalized cyclosilanes depends on both conformation and connectivity. Borane-catalyzed dehydrocoupling of thiophenols with partially hydrogenated cyclosilanes proceeded with high chemoselectivity for Si–H bonds in the presence of Si–Si bonds. Isomeric 1,3- and 1,4-functionalized cyclosilanes afforded isomeric cyclosilane thioethers that also differed in preference for chair or twist-boat conformations as demonstrated by both X-ray crystal structures and density functional theory (DFT) calculations. Here, the confounding effects of different conformations and connectivity could be distinguished with time-dependent DFT (TD-DFT) calculations and validated with experimentally obtained UV–vis spectra.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0020681

OSTI ID:: 1900518

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 23 Vol. 41; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

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
Boracyclopentasilane, a New Type of Heterocyclic Silane Hengge, Edwin; Wolfer, Dieter Angewandte Chemie International Edition in English, Vol. 12, Issue 4 https://doi.org/10.1002/anie.197303151	journal	April 1973
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
Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes Kanazawa, Yuki; Tsuji, Hayato; Ehara, Masahiro ChemPhysChem, Vol. 17, Issue 19 https://doi.org/10.1002/cphc.201600633	journal	August 2016
Exploiting catalytic dehydrogenative coupling in the synthesis and study of polysilanes Rosenberg, Lisa Macromolecular Symposia, Vol. 196, Issue 1 https://doi.org/10.1002/masy.200390173	journal	July 2003
Reactions of alkenylpolysilanes catalyzed by some noble metal salts Yamamoto, Keiji; Kumada, Makoto; Nakajima, Isao Journal of Organometallic Chemistry, Vol. 13, Issue 2 https://doi.org/10.1016/S0022-328X(00)82761-8	journal	August 1968
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
Molecular Silicon Clusters Heider, Yannic; Scheschkewitz, David Chemical Reviews, Vol. 121, Issue 15 https://doi.org/10.1021/acs.chemrev.1c00052	journal	June 2021
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
Tunable SiN Hybrid Conjugated Materials Folster, Carlton P.; Nguyen, Phi N.; Siegler, Maxime A. Organometallics, Vol. 38, Issue 15 https://doi.org/10.1021/acs.organomet.9b00254	journal	July 2019
Selective free-radical halogenation of poly(phenylsilane) Banovetz, John P.; Hsiao, Yu Ling; Waymouth, Robert M. Journal of the American Chemical Society, Vol. 115, Issue 6 https://doi.org/10.1021/ja00059a077	journal	March 1993
Chemistry of organosilicon compounds. 303. The missing hexasilaprismane: synthesis, x-ray analysis and photochemical reactions Sekiguchi, Akira; Yatabe, Tetsuo; Kabuto, Chizuko Journal of the American Chemical Society, Vol. 115, Issue 13 https://doi.org/10.1021/ja00066a075	journal	June 1993
Free-Radical Hydrosilylation of Poly(phenylsilane): Synthesis of Functional Polysilanes Hsiao, Yu-Ling; Waymouth, Robert M. Journal of the American Chemical Society, Vol. 116, Issue 21 https://doi.org/10.1021/ja00100a065	journal	October 1994
Cyclic polysilanes. IV. Anion radicals and spectroscopic properties of the permethylcyclopolysilanes Carberry, Edward A.; West, Robert; Glass, Gary E. Journal of the American Chemical Society, Vol. 91, Issue 20 https://doi.org/10.1021/ja01048a008	journal	September 1969
Cleavage of Symmetrically Substituted Disilanes by Lithium in Tetrahydrofuran Gilman, Henry; Lichtenwalter, Glen D. Journal of the American Chemical Society, Vol. 80, Issue 3 https://doi.org/10.1021/ja01536a025	journal	February 1958
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
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
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
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
Borane-catalysed postpolymerisation modification of the Si–H bonds in poly(phenylsilane) Lee, P. T. K.; Rosenberg, L. Dalton Transactions, Vol. 46, Issue 27 https://doi.org/10.1039/C7DT00546F	journal	January 2017
Metallocene influence on poly(cyclosilane) structure and properties Folster, Carlton P.; Klausen, Rebekka S. Polymer Chemistry, Vol. 9, Issue 15 https://doi.org/10.1039/C8PY00312B	journal	January 2018
Reductive halocyclosilazane polymerization Folster, Carlton P.; Nguyen, Phi N.; Klausen, Rebekka S. Dalton Transactions https://doi.org/10.1039/C9DT04468J	journal	January 2020
Long-range coupling in cyclic silanes Ferguson, John T.; Jiang, Qifeng; Marro, Eric A. Dalton Transactions, Vol. 49, Issue 42 https://doi.org/10.1039/D0DT03163A	journal	January 2020
Effect of polycyclosilane microstructure on thermal properties Jiang, Qifeng; Wong, Sydnee; Klausen, Rebekka S. Polymer Chemistry, Vol. 12, Issue 33 https://doi.org/10.1039/D1PY00383F	journal	January 2021
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
Open, cyclic, and bicyclic compounds of double silylated phosphorus and boron Markov, Jelena; Fischer, Roland; Wagner, Harald Dalton Transactions, Issue 14 https://doi.org/10.1039/b404073b	journal	January 2004
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
Ring contraction of cyclohexasilanes to silylcyclopentasilanes and the preparation of monofunctional nonamethylcyclopentasilanes Ishikawa, M.; Kumada, M. Journal of the Chemical Society D: Chemical Communications, Issue 10 https://doi.org/10.1039/c2969000567b	journal	January 1969
Luminescence properties of a cubic silicon cluster octasilacubane Kanemitsu, Yoshihiko; Suzuki, Katsunori; Kondo, Michio Physical Review B, Vol. 51, Issue 16 https://doi.org/10.1103/PhysRevB.51.10666	journal	April 1995
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

Similar Records

Poly(cyclosilane) Connectivity Tunes Optical Absorbance

Journal Article · Mon Apr 25 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1864628

Poly(cyclosilane) Postpolymerization Hydrosilylation

Journal Article · Fri Apr 19 00:00:00 EDT 2024 · Macromolecules · OSTI ID:2338167

Investigating the Microstructure of Poly(cyclosilane) by ²⁹Si Solid-State NMR Spectroscopy and DFT Calculations

Journal Article · Mon Oct 14 00:00:00 EDT 2019 · Chemistry of Materials · OSTI ID:1570241

Related Subjects

36 MATERIALS SCIENCE
Chemical calculations
Conformation
Molecular structure
Silicon
Sulfur

CCDC 2206153: Experimental Crystal Structure Determination F., Gittens, Alexandra; Qifeng, Jiang,; A., Siegler, Maxime https://doi.org/10.5517/ccdc.csd.cc2d1p7d The current record is supplemented by this dataset	dataset	January 2022
CCDC 2206154: Experimental Crystal Structure Determination F., Gittens, Alexandra; Qifeng, Jiang,; A., Siegler, Maxime https://doi.org/10.5517/ccdc.csd.cc2d1p8f The current record is supplemented by this dataset	dataset	January 2022
CCDC 2206155: Experimental Crystal Structure Determination F., Gittens, Alexandra; Qifeng, Jiang,; A., Siegler, Maxime https://doi.org/10.5517/ccdc.csd.cc2d1p9g The current record is supplemented by this dataset	dataset	January 2022
CCDC 2209879: Experimental Crystal Structure Determination F., Gittens, Alexandra; Qifeng, Jiang,; A., Siegler, Maxime https://doi.org/10.5517/ccdc.csd.cc2d5kfl The current record is supplemented by this dataset	dataset	January 2022

Conjugation in Isomeric Cyclosilane Thioethers

Citation Formats

References (32)

Linked Research (4)

Similar Records

Related Subjects