{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T20:52:09Z","timestamp":1792011129077,"version":"4.4.0"},"reference-count":58,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2020,12,10]],"date-time":"2020-12-10T00:00:00Z","timestamp":1607558400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2021,2,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Thermolysis of tris(silyl) tin hydride <jats:bold>2<\/jats:bold> at 70\u2009\u00b0C for 3\u2005hours results in elimination of tBu<jats:sub>2<\/jats:sub>MeSiH and generation of bis(silyl) stannylene <jats:bold>3<\/jats:bold> which dimerizes instantaneously yielding distannene <jats:bold>4<\/jats:bold>. Compound <jats:bold>3<\/jats:bold> can be trapped by NHC<jats:sup>Me<\/jats:sup> yielding stannylene\u2010NHC<jats:sup>Me<\/jats:sup> complex <jats:bold>5<\/jats:bold>. Upon heating (70\u2009\u00b0C, 24\u2005h) <jats:bold>4<\/jats:bold> yields stannyl radical <jats:bold>8<\/jats:bold> along with pentastannatricyclo[2.1.0.0<jats:sup>2,\u20095<\/jats:sup>]pentane <jats:bold>10<\/jats:bold> (ca. 30\u2009%) and traces (ca. 5\u2009%) of the novel octastannacubane <jats:bold>9<\/jats:bold>. Remarkably, octastannacubane <jats:bold>9<\/jats:bold> is produced in 70\u2009% yield by mild heating (50\u2009\u00b0C) of 1,1,2,2\u2010tetrasilyldistannane <jats:bold>11<\/jats:bold>, along with tBu<jats:sub>2<\/jats:sub>MeSiH. Octastannacubane <jats:bold>9<\/jats:bold> was characterized by X\u2010ray crystallography, NMR and UV\/Vis spectroscopy. Based on DFT quantum\u2010mechanical calculations the <jats:bold>11<\/jats:bold> \u2192 <jats:bold>9<\/jats:bold> transformation occurs via reductive elimination of two tBu<jats:sub>2<\/jats:sub>MeSiH molecules from <jats:bold>11<\/jats:bold> yielding a distannyne, (or its bis\u2010stannylene isomer), followed by its tetramerization.<\/jats:p>","DOI":"10.1002\/anie.202013007","type":"journal-article","created":{"date-parts":[[2020,11,3]],"date-time":"2020-11-03T19:06:10Z","timestamp":1604430370000},"page":"2898-2902","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["A High Yield Synthesis of an Octastannacubane and a Bis(silyl) Stannylene via Reductive Elimination of a Silane"],"prefix":"10.1002","volume":"60","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8549-7989","authenticated-orcid":false,"given":"Roman","family":"Bashkurov","sequence":"first","affiliation":[{"name":"Schulich Faculty of Chemistry Technion-Israel Institute of Technology  Haifa 32000 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yosi","family":"Kratish","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion-Israel Institute of Technology  Haifa 32000 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalia","family":"Fridman","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion-Israel Institute of Technology  Haifa 32000 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dmitry","family":"Bravo\u2010Zhivotovskii","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion-Israel Institute of Technology  Haifa 32000 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1923-9236","authenticated-orcid":false,"given":"Yitzhak","family":"Apeloig","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry Technion-Israel Institute of Technology  Haifa 32000 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,12,10]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500523x"},{"key":"e_1_2_2_2_1","unstructured":"\u00a0"},{"key":"e_1_2_2_3_2","doi-asserted-by":"crossref","first-page":"935","DOI":"10.1002\/0470857188.ch15","volume-title":"The Chemistry of Organic Germanium, Tin and Lead Compounds, Vol.\u20052","author":"Sekiguchi A.","year":"2002"},{"key":"e_1_2_2_4_2","first-page":"49","volume-title":"Functional Molecular Silicon Compounds\u2005II: Low Oxidation States, Vol.\u2005156","author":"Unno M.","year":"2014"},{"key":"e_1_2_2_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01069a041"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.8b00888"},{"key":"e_1_2_2_7_1","unstructured":"\u00a0"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39880001083"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199213541"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921041033"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00041a063"},{"key":"e_1_2_2_11_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.73.2093"},{"key":"e_1_2_2_12_1","unstructured":"\u00a0"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00161a008"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00005a074"},{"key":"e_1_2_2_15_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb-1999-0709"},{"key":"e_1_2_2_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010216)40:4<796::AID-ANIE7960>3.0.CO;2-5"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010216)113:4<818::AID-ANGE8180>3.0.CO;2-0"},{"key":"e_1_2_2_17_1","unstructured":"In one case that of octasilacubane a high yield of 72\u2009% was reported. See ref.\u2005[5a]."},{"key":"e_1_2_2_18_1","unstructured":"\u00a0"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00198a085"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00044a011"},{"key":"e_1_2_2_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/9780470669266"},{"key":"e_1_2_2_22_1","first-page":"397","volume-title":"Organotransition Metal Chemistry From Bonding to Catalysis","author":"Hartwig J. F.","year":"2010"},{"key":"e_1_2_2_23_1","unstructured":"\u00a0"},{"key":"e_1_2_2_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om960289m"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja963237x"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990418"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201605317"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00572"},{"key":"e_1_2_2_29_1","unstructured":"\u00a0"},{"key":"e_1_2_2_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2017.09.052"},{"key":"e_1_2_2_31_2","unstructured":"R. Bashkurov M.Sc. thesis Technion-Israel Institute of Technology (Haifa Israel) 2019;"},{"key":"e_1_2_2_32_2","unstructured":"We developed an improved synthesis of2(see SI and ref.\u2005[14b])."},{"key":"e_1_2_2_33_1","unstructured":"\u00a0"},{"key":"e_1_2_2_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja040152k"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja063322x"},{"key":"e_1_2_2_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900093s"},{"key":"e_1_2_2_37_1","unstructured":"Deposition Numbers 1990645 (for5) and 1990646 (for9)contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures servicewww.ccdc.cam.ac.uk\/structures."},{"key":"e_1_2_2_38_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2003.12.025"},{"key":"e_1_2_2_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527600043"},{"key":"e_1_2_2_40_1","unstructured":"All calculations were done using Gaussian 09 Rev. D1 software. All calculations were performed using Density Functional Theory using the B3PW91-D3\/6\u2013311+G(d p) [H C Si] SDD [Sn]\/\/B3PW91-D3\/6-31G(d p) [H C Si] SDD [Sn] level of theory; further computational details and a full reference list for the methods used are provided in the SI."},{"key":"e_1_2_2_41_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb-2004-11-1215"},{"key":"e_1_2_2_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/om050835o"},{"key":"e_1_2_2_43_1","doi-asserted-by":"crossref","unstructured":"M. Walewska J. Hlina W. Gaderbauer H. Wagner J. Baumgartner C. Marschner Z. Anorg. Allg. Chem.2016 642 1304\u20131313.","DOI":"10.1002\/zaac.201600284"},{"key":"e_1_2_2_44_1","unstructured":"119Sn chemical shifts of diamagnetic tin compounds cover a range of approximately 6500\u2005ppm from ca. +4000 to \u22122500. Such a large range of chemical shifts indicates great sensitivity of this parameter even to small structural and substituent changes. See ref.\u2005[25]."},{"key":"e_1_2_2_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/9780470758090.ch1"},{"key":"e_1_2_2_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja030156"},{"key":"e_1_2_2_47_1","unstructured":"IUPAC name octakis(di-tert-butyl(methyl)silyl)pentacyclo [4.2.0.02 5.03 8.04 7]octastannacubane."},{"key":"e_1_2_2_48_1","unstructured":"A few examples of tricyclo[2.1.0.02 5]pentane derivatives fully or partially composed of heavy group\u200514 elements were previously reported:"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja020574z"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900567"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja401650q"},{"key":"e_1_2_2_52_1","unstructured":"Disappointingly we were unable to measure the expected2J(119Sn-117Sn) and3J(119Sn-117Sn) coupling constants; probably the2Jcoupling constants are poorly resolved and the value of3Jis smaller than the line width of the parent peak (w1\/2=67\u2005Hz)."},{"key":"e_1_2_2_53_1","unstructured":"Based on the different Sn\u2212Sn\u2212Si bond angles in the X-ray structure of9 it was expected that the Si atoms would be magnetically not equivalent. However the29Si NMR spectrum revealed a single resonance indicating the magnetic equivalence of all silyl substituents on the NMR time scale. Similarly a single resonance was reported for the silyl substituents in persilyl substituted octasilacubane (see ref.\u2005[5a])."},{"key":"e_1_2_2_54_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5SC02707A"},{"key":"e_1_2_2_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0257164"},{"key":"e_1_2_2_56_1","unstructured":"The calculations also show that the 1 1-silane elimination pathway is preferred over the 1 2-silane elimination route. The alternative 1 2-elimination to give a distannene followed by 1 2-elimination of a second silane molecule also yielding distannyne intermediates13\u2032or14\u2032 have similar thermodynamic energies to the 1 1-elimination route (see SI). However the activation barrier for the 1 2-Me3SiH elimination from11\u2032(\u0394G\u2260=46.4\u2005kcal\u2009mol\u22121; \u0394H\u2260=46.1\u2005kcal\u2009mol\u22121;T\u0394S\u2260=\u22120.3\u2005kcal\u2009mol\u22121) is significantly higher than for the 1 1-elimination ruling out this competing pathway."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202013007","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202013007","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202013007","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,3]],"date-time":"2023-09-03T04:27:38Z","timestamp":1693715258000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202013007"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,12,10]]},"references-count":58,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2021,2,8]]}},"alternative-id":["10.1002\/anie.202013007"],"URL":"https:\/\/doi.org\/10.1002\/anie.202013007","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,12,10]]},"assertion":[{"value":"2020-09-25","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2020-12-10","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}