{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T09:01:52Z","timestamp":1760346112741},"reference-count":38,"publisher":"American Chemical Society (ACS)","issue":"33","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Am. Chem. Soc."],"published-print":{"date-parts":[[2009,8,26]]},"DOI":"10.1021\/ja905097b","type":"journal-article","created":{"date-parts":[[2009,7,31]],"date-time":"2009-07-31T11:53:19Z","timestamp":1249041199000},"page":"11698-11700","source":"Crossref","is-referenced-by-count":24,"title":["Isolable Photoreactive Polysilyl Radicals"],"prefix":"10.1021","volume":"131","author":[{"given":"Gregory","family":"Molev","sequence":"first","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Boris","family":"Tumanskii","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dennis","family":"Sheberla","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mark","family":"Botoshansky","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dmitry","family":"Bravo-Zhivotovskii","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yitzhak","family":"Apeloig","sequence":"additional","affiliation":[{"name":"Schulich Faculty of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"316","published-online":{"date-parts":[[2009,7,31]]},"reference":[{"key":"ref1\/cit1a","doi-asserted-by":"crossref","first-page":"128","DOI":"10.1246\/cl.2008.128","volume":"37","author":"Lee V. Ya.","year":"2008","journal-title":"Chem. Lett."},{"key":"ref1\/cit1b","first-page":"1209","author":"Sekiguchi A.","year":"2005","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref1\/cit1c","doi-asserted-by":"crossref","DOI":"10.1002\/0470024755","volume-title":"Organosilanes in Radical Chemistry","author":"Chatgilialoglu C.","year":"2004"},{"key":"ref1\/cit1d","doi-asserted-by":"crossref","first-page":"789","DOI":"10.1021\/cr020406p","volume":"103","author":"Power P.","year":"2003","journal-title":"Chem. Rev."},{"key":"ref1\/cit1e","doi-asserted-by":"crossref","first-page":"410","DOI":"10.1021\/ar6000473","volume":"40","author":"Lee V. Ya.","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"ref1\/cit1f","volume-title":"Reviews of Reactive Intermediates Chemistry","author":"Lee V. Ya.","year":"2007"},{"key":"ref1\/cit1g","doi-asserted-by":"crossref","first-page":"2310","DOI":"10.1002\/chem.200701415","volume":"14","author":"Chatgilialoglu C.","year":"2008","journal-title":"Chem.\u2014Eur. J."},{"key":"ref1\/cit1h","doi-asserted-by":"crossref","first-page":"2066","DOI":"10.1039\/b602883g","author":"Zhu Z. Y.","year":"2006","journal-title":"Chem. Commun."},{"key":"ref2\/cit2a","doi-asserted-by":"crossref","first-page":"1443","DOI":"10.1021\/cr00037a014","volume":"95","author":"Birot M.","year":"1995","journal-title":"Chem. Rev."},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"4669","DOI":"10.1039\/B609412K","author":"Luh T. Y.","year":"2006","journal-title":"Chem. Commun"},{"key":"ref2\/cit2c","unstructured":"cKravchenko, V., Bravo-Zhivotovskii, D., Tumanskii, B., Botoshansky, M., Segal, N., Molev, G., Kosa, M., and Apeloig, Y.InOrganosilicon Chemistry VI: From Molecules to Materials;Auner, N. and Weis, J.,Eds.Wiley-VCH: Weinheim, 2005; p48."},{"key":"ref2\/cit2d","volume-title":"Handbook of Photochemistry and Photobiology","author":"Kira M."},{"key":"ref2\/cit2e","doi-asserted-by":"crossref","first-page":"999","DOI":"10.1351\/pac200375080999","volume":"75","author":"Fogarty H. A.","year":"2003","journal-title":"Pure Appl. Chem."},{"key":"ref2\/cit2f","doi-asserted-by":"crossref","first-page":"425","DOI":"10.1007\/BF03162156","volume":"18","author":"Apeloig Y.","year":"2000","journal-title":"Appl. Magn. Reson."},{"key":"ref2\/cit2g","doi-asserted-by":"crossref","first-page":"257","DOI":"10.1016\/S0009-2614(03)00717-6","author":"Azinovic D.","year":"2003","journal-title":"Chem. Phys. Lett."},{"key":"ref3\/cit3","doi-asserted-by":"crossref","first-page":"3886","DOI":"10.1021\/jo0017988","volume":"66","author":"Canepa M.","year":"2001","journal-title":"J. Org. Chem."},{"key":"ref4\/cit4","doi-asserted-by":"crossref","first-page":"9865","DOI":"10.1021\/ja0126780","volume":"124","author":"Sekiguchi A.","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref5\/cit5","unstructured":"Synthesis of1: a hexane solution (4 mL) oft-Bu2MeSiLi (B) (0.5 g, 3.0 mmol) was added to a frozen hexane solution (10 mL) of (t-Bu2MeSi)2HSiSiHCl2(A) (0.44 g, 1.0 mmol). The frozen mixture was warmed up to 0 \u00b0C and stirred for 1 h in the dark. All volatile compounds were then evaporated in vacuum, and 5 mL of dry hexane were added. Keeping the solution at \u221230\u00b0C for 12 h yielded 0.45 g (65%) of orange prisms (Figure 1a, insert) identified as1by X-ray crystallography (Figure S1), EPR spectroscopy (Figure 1a), trapping reactions (Scheme 1, paths a, b),and non-preparative synthesis from other precursors (Scheme 1, paths c, d); UV\u2212vis (Figure 3a): 230 nm (9300), 268 nm (13130), 278 nm (12200), 350 nm (3360), 428 nm (800)."},{"key":"ref6\/cit6","unstructured":"Radical2was obtained previously in 44% yield.4The EPR spectra of2at high resolution and in toluene glass (not reported previously) are given inFigures S5 and S6, respectively."},{"key":"ref7\/cit7","unstructured":"The following radicals were prepared using eq 1: (i-Pr3Si)3Si\u00b7, R(t-Bu2MeSi)2Si\u00b7(R = Ph; 2,4,6-trimethylphenyl; (Me3Si)3Si; (i-Pr3Si)2HSi). The synthesis and spectroscopy of these radicals will be reported elsewhere."},{"key":"ref8\/cit8","unstructured":"SeeSupporting Informationfor the CIF file and experimental details (Figure S2)."},{"key":"ref9\/cit9","unstructured":"The EPR spectrum of1in toluene glass at 130 K (Figure S7) shows low anisotropy of the axialg-factor tensor (g\u22a5= 2.0068,g\u2225= 2.0034) and high anisotropy of the hyperfine coupling tensor with the29Si\u03b1nuclei:A\u22a5\u2248 0 G,A\u2225(29Si\u03b1) = 113 G."},{"key":"ref10\/cit10","unstructured":"Radical3was synthesized by the reaction of (i-Pr3Si)2HSiSiCl2H withi-Pr3SiLi, i.e., using eq 1; see theSupporting Information."},{"key":"ref11\/cit11","volume-title":"Electron Paramagnetic Resonance","author":"Weil J. A.","year":"2007","edition":"2"},{"key":"ref12\/cit12a","doi-asserted-by":"crossref","first-page":"7791","DOI":"10.1021\/ja00493a001","volume":"100","author":"Stanislavski D. A.","year":"1978","journal-title":"J. Am. Chem. Soc."},{"key":"ref12\/cit12b","doi-asserted-by":"crossref","first-page":"1323","DOI":"10.1246\/cl.1974.1323","volume":"3","author":"Sakurai H.","year":"1974","journal-title":"Chem. Lett."},{"key":"ref12\/cit12c","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1016\/0022-328X(87)87156-5","volume":"336","author":"Jackson R. A.","year":"1987","journal-title":"J. Organomet. Chem."},{"key":"ref13\/cit13","unstructured":"Calculations were carried out at the UB3LYP\/TZVP\/\/UB3LYP\/6-31G(d) level using the Gaussian 03, Revision D.02 series of programs: Frisch, M. J.; et al.Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004, (see theSupporting Informationfor the full list of authors and for the calculations\u2019 details)."},{"key":"ref14\/cit14","doi-asserted-by":"crossref","first-page":"846","DOI":"10.1021\/ja00733a008","volume":"93","author":"Krusic P. J.","year":"1971","journal-title":"J. Am. Chem. Soc."},{"key":"ref15\/cit15","doi-asserted-by":"crossref","first-page":"9626","DOI":"10.1021\/ja040079y","volume":"126","author":"Sekiguchi A.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref16\/cit16a","doi-asserted-by":"crossref","first-page":"3530","DOI":"10.1002\/chem.200204643","volume":"9","author":"Takeda N.","year":"2003","journal-title":"Chem.\u2014Eur. J."},{"key":"ref16\/cit16b","volume-title":"The Chemistry of Organic Silicon Compounds","author":"Gaspar P. P.","year":"1998"},{"key":"ref17\/cit17","unstructured":"The experiment was carried out in the EPR tube upon irradiation with a 1 kW mercury lamp inside the cavity of an EPR spectrometer. Full conversion of1under these conditions occurs in 200 s. We note that the recorded second-order decay of1upon irradiation is not proof for the bimolecular reaction since the quantum yield of the reaction was not measured. The kinetic curves are given inFigure S8."},{"key":"ref18\/cit18","unstructured":"In radical2onlythe SOMO-1 \u2192 SOMO transition occurs upon irradiation with \u03bb > 400 nm. In radical1both SOMO-1 \u2192 SOMO and SOMO \u2192 LUMO transitions occur, and therefore photoexcited1may exhibit enhanced electron-donating properties (Figure S9)."},{"key":"ref19\/cit19","doi-asserted-by":"crossref","first-page":"681","DOI":"10.1103\/RevModPhys.73.681","volume":"73","author":"Heeger A. J.","year":"2001","journal-title":"Rev. Mod. Phys"},{"key":"ref20\/cit20","unstructured":"Related (not photoinduced) mechanism of hydrogen abstraction by organic radicals was reported:"},{"key":"ref20\/cit20a","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1021\/ar0682029","volume":"40","author":"Litwinienko G.","year":"2007","journal-title":"Acc. Chem. Res."},{"key":"ref20\/cit20b","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1146\/annurev.physchem.55.091602.094446","volume":"55","author":"Mayer J. M.","year":"2004","journal-title":"Annu. Rev. Phys. Chem."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja905097b","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,15]],"date-time":"2023-03-15T23:56:34Z","timestamp":1678924594000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja905097b"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,7,31]]},"references-count":38,"journal-issue":{"issue":"33","published-print":{"date-parts":[[2009,8,26]]}},"alternative-id":["10.1021\/ja905097b"],"URL":"https:\/\/doi.org\/10.1021\/ja905097b","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,7,31]]}}}