none 10.1002/anie.202006283 Wiley Wiley (John Wiley & Sons) 311 116352885 89 2023090122205200258 10.1002 2023-09-03T02:34:41Z 2020-05-14T22:27:55Z 41 Angewandte Chemie International Edition Angew Chem Int Ed 1433-7851 1521-3773 08 24 2020 59 35 10.1002/anie.v59.35 https://onlinelibrary.wiley.com/toc/15213773/59/35 Cem B. Yildiz Department of Aromatic and Medicinal Plants Aksaray University 68100 Aksaray Turkey http://orcid.org/0000-0002-0424-4673 Kinga I. Leszczyńska Krupp-Chair of Inorganic and General Chemistry Saarland University 66123 Saarbrücken Germany http://orcid.org/0000-0002-1117-8934 Sandra González‐Gallardo Krupp-Chair of Inorganic and General Chemistry Saarland University 66123 Saarbrücken Germany http://orcid.org/0000-0002-2930-9074 Michael Zimmer Krupp-Chair of Inorganic and General Chemistry Saarland University 66123 Saarbrücken Germany http://orcid.org/0000-0002-0406-236X Akin Azizoglu Department of Chemistry Faculty of Science and Letters University of Balıkesir 10145 Balıkesir Turkey http://orcid.org/0000-0002-5098-1842 Till Biskup Chair of Physical Chemistry and Chemical Education Saarland University 66123 Saarbrücken Germany Christopher W. M. Kay Chair of Physical Chemistry and Chemical Education Saarland University 66123 Saarbrücken Germany London Centre for Nanotechnology University College London 17–19 Gordon Street London WC1H 0AH UK http://orcid.org/0000-0002-5200-6004 Volker Huch Krupp-Chair of Inorganic and General Chemistry Saarland University 66123 Saarbrücken Germany http://orcid.org/0000-0001-5337-5613 Henry S. Rzepa Department of Chemistry Imperial College London MSRH, White City Campus, 80 Wood Lane London W12 0BZ UK http://orcid.org/0000-0002-8635-8390 David Scheschkewitz Krupp-Chair of Inorganic and General Chemistry Saarland University 66123 Saarbrücken Germany http://orcid.org/0000-0001-5600-8034 Abstract Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c ‐Si 3 Tip 4 (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c ‐[(CR 2 CH 2 )(N t Bu) 2 ]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c ‐(CH) 2 (N t Bu) 2 Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate. 06 15 2020 08 24 2020 15087 15092 10.1002/anie.202006283 2 10.1002/crossmark_policy onlinelibrary.wiley.com true 2020-04-30 2020-06-15 Deutscher Akademischer Austauschdienst https://doi.org/10.13039/501100001655 Türkiye Bilimsel ve Teknolojik Araştirma Kurumu https://doi.org/10.13039/501100004410 2214-A http://creativecommons.org/licenses/by-nc-nd/4.0/ 10.1002/anie.202006283 https://onlinelibrary.wiley.com/doi/10.1002/anie.202006283 https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202006283 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.202006283 https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202006283 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202006283   10.1021/cr00028a002 10.1039/c2cs00005a 10.1021/acs.chemrev.9b00260 10.1021/cr400056a   10.1039/C1CS15165G 10.1039/C5CS00051C 10.1016/j.chempr.2019.03.018   Reactive Intermediate Chemistry Newcomb M. 2004 10.1039/C5CS00739A 10.1002/cber.19150480189   10.1021/ja972977i 10.1021/ja026301l 10.1021/ja00213a006 10.1021/ar00003a005 10.1021/ja992507j   10.1002/anie.199505551 10.1002/ange.19951070523 10.1126/science.1068167 10.1021/cr020406p 10.1002/anie.201103742 10.1002/ange.201103742 10.1002/anie.201208360 10.1002/ange.201208360 Comprehensive Inorganic Chemistry II, Vol. 1. 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