Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/34447
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dc.contributor.authorLee, F.Y.en_US
dc.contributor.author林寬鋸zh_TW
dc.contributor.authorHuang, J.J.en_US
dc.contributor.authorChen, Y.J.en_US
dc.contributor.authorLin, K.J.en_US
dc.contributor.authorLee, G.H.en_US
dc.contributor.authorPeng, S.M.en_US
dc.contributor.authorHwu, J.R.en_US
dc.contributor.authorLu, K.L.en_US
dc.date2005zh_TW
dc.date.accessioned2014-06-06T07:47:44Z-
dc.date.available2014-06-06T07:47:44Z-
dc.identifier.issn0022-328Xzh_TW
dc.identifier.urihttp://hdl.handle.net/11455/34447-
dc.description.abstractThe reaction Of Os-3(CO)(12) with an excess of 1-hydroxypyridine-2-thione and Me3NO gives three mononuclear osmium complexes Os(CO)(2) (eta(2) -SC5H4N(O))(2) (1), Os(CO)(2)( eta(2)-SC5H4N(O))(eta(2)-SC5H4N) (2), and Os(CO)(2)(eta(2) -SC5H4N)(2) (3). The results of single-crystal X-ray analyses reveal that complex 1 contains two O,S-chelate pyridine-2-thione N-oxide (PyOS) ligands, whereas complex 2 contains one O,S-chelate PyOS and one N,S-chelate pyridine-2-thiolate group. The unique structure of 2 provides evidence of the pathway for this transformation. When this reaction was monitored by H-1 NMR spectroscopy the triosmium complexes Os-3(CO)(10)(mu-H)( mu-eta'-S-C5H4N(O)) (4) and Os-3(CO)(9)(mu-H)(mu-eta(1): eta2-SC5H4N(O)) (5) were identified as intermediates in the formation of the mononuclear final products 1-3. The proposed pathway is further supported by the observation of several dinu-clear osmium intermediates by electrospray ionization mass spectrometry. In addition, the reaction of Os-3(CO)(12) with 1-hydroxypyridine-2-thione in the absence of Me3NO at 90degreesC generated mononuclear complex 2 as the major product along with smaller amounts of complexes 1 and 3. These results suggest that the N-oxide facilitates the decarbonylation reaction. Crystal data for 1: monoclinic, space group C2/c, a = 26.9990(5) A, b = 7.6230(7) A, c = 14.2980(13) A, beta =101.620(2)degrees, V= 2882.4(4) A(3), Z = 8. Crystal data for 2: monoclinic, space group C2/c, a = 5.7884(3) angstrom, b = 13.9667(7) angstrom, c = 17.2575(9) A, beta = 96.686(l)degrees, V= 1385.69(12) angstrom (3), Z = 4. (C) 2004 Elsevier B.V. All rights reserved.en_US
dc.language.isoen_USzh_TW
dc.relationJournal of Organometallic Chemistryen_US
dc.relation.ispartofseriesJournal of Organometallic Chemistry, Volume 690, Issue 2, Page(s) 441-449.en_US
dc.relation.urihttp://dx.doi.org/10.1016/j.jorganchem.2004.09.064en_US
dc.subjectosmiumen_US
dc.subjectclusteren_US
dc.subjectN-oxide liganden_US
dc.subjecttransformationen_US
dc.subjectcrystal structureen_US
dc.subjectintermediateen_US
dc.subjectelectrospray mass-spectrometryen_US
dc.subjectx-ray crystalen_US
dc.subjecttriosmium clustersen_US
dc.subjectmolecular-structuresen_US
dc.subjectorganometallic chemistryen_US
dc.subjectisocyanide complexesen_US
dc.subjectthiolate complexesen_US
dc.subjectc-hen_US
dc.subjectliganden_US
dc.subjectcoordinationen_US
dc.titleOs(CO)(2)(eta(2)-SC5H4N(O))(eta(2)-SC5H4N): structural evidence for the transformation of pyridine-2-thione N-oxide to pyridine-2-thiolate in osmium complexesen_US
dc.typeJournal Articlezh_TW
dc.identifier.doi10.1016/j.jorganchem.2004.09.064zh_TW
item.grantfulltextnone-
item.openairetypeJournal Article-
item.languageiso639-1en_US-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.cerifentitytypePublications-
item.fulltextno fulltext-
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