DC Field | Value | Language |
---|---|---|
dc.contributor.author | Park, Joon Taik | ko |
dc.contributor.author | Chung, JH | ko |
dc.contributor.author | Song, Hyunjoon | ko |
dc.contributor.author | Lee, K | ko |
dc.contributor.author | Lee, JH | ko |
dc.contributor.author | Park, JR | ko |
dc.contributor.author | Suh, IH | ko |
dc.date.accessioned | 2013-03-02T20:00:10Z | - |
dc.date.available | 2013-03-02T20:00:10Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 1996-12 | - |
dc.identifier.citation | JOURNAL OF ORGANOMETALLIC CHEMISTRY, v.526, no.2, pp.215 - 225 | - |
dc.identifier.issn | 0022-328X | - |
dc.identifier.uri | http://hdl.handle.net/10203/75269 | - |
dc.description.abstract | Initial decarbonylation of CpWOs(3)(CO)(11)(mu(3)-CTol) (1; Cp = eta(5)-C5H5, Tol = p-C(6)H(4)Me) with Me(3)NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido complex CpWOs(3)(CO)(10)(mu(3)-CTol)(mu-H)(2) (2), a 'butterfly' cluster with a 60 valence electron (VE), and an oxo complex CpWOs(3)(CO)(10)(mu-O)(mu(3)-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh(3) to afford a 62 VE 'butterfly' complex CpWOs(3)(CO)(10)(PPh(3))(mu(3)-CTol)(mu-H)(2) (6). Thermolysis of 2 in the presence of water gives a hydride oxo alkylidene complex, syn-CpWOs(3)(CO)(9)(mu-O)(mu-CHTol)(mu-H) (3a), in which the tolyl substituent on the alkylidene carbon is oriented syn to the mu-oxo ligand, Thermolysis of 4 at 110 degrees C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs(3)(CO)(9)(mu-O)(mu(3)-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydride oxo alkylidene complexes, anti-CpWOs(3)(CO)(9)(mu-O)(mu-CHTol)(mu-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5 and 6 have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, H-1 and C-13 NMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell parameters a = 14.18(1), b = 28.46(1), c = 13.59(3) Angstrom, V = 5484(13)Angstrom(3) and Z = 8. Compound 6 crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 19.298(2), b = 22.406(4), c = 9.364(1)Angstrom, beta = 92.83(9)degrees, V = 4044.0(9)Angstrom(3) and Z = 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a 'butterfly' WOs3 metal core with a respective dihedral angle of 114.3(2)degrees and 113.6(4)degrees between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)(3) units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh(3). The mu(3)-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes. | - |
dc.language | English | - |
dc.publisher | ELSEVIER SCIENCE SA LAUSANNE | - |
dc.subject | OSMIUM CARBONYL HYDRIDES | - |
dc.subject | O BOND SCISSION | - |
dc.subject | CRYSTAL-STRUCTURE | - |
dc.subject | TRIOSMIUM CLUSTER | - |
dc.subject | SOLUTION DYNAMICS | - |
dc.subject | ACYL LIGAND | - |
dc.subject | COMPLEXES | - |
dc.subject | METAL | - |
dc.subject | ALKYLIDENE | - |
dc.subject | CPWOS3(CO)9(MU-O)(MU-3-CCH2TOL) | - |
dc.title | Characterization and structures of intermediates in the reactivity of CpWOs(3)(CO)(11)(mu(3)-CTol) towards dihydrogen and water | - |
dc.type | Article | - |
dc.identifier.wosid | A1996WB28400002 | - |
dc.identifier.scopusid | 2-s2.0-0030604334 | - |
dc.type.rims | ART | - |
dc.citation.volume | 526 | - |
dc.citation.issue | 2 | - |
dc.citation.beginningpage | 215 | - |
dc.citation.endingpage | 225 | - |
dc.citation.publicationname | JOURNAL OF ORGANOMETALLIC CHEMISTRY | - |
dc.contributor.localauthor | Park, Joon Taik | - |
dc.contributor.localauthor | Song, Hyunjoon | - |
dc.contributor.nonIdAuthor | Chung, JH | - |
dc.contributor.nonIdAuthor | Lee, K | - |
dc.contributor.nonIdAuthor | Lee, JH | - |
dc.contributor.nonIdAuthor | Park, JR | - |
dc.contributor.nonIdAuthor | Suh, IH | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordAuthor | tungsten-triosmium | - |
dc.subject.keywordAuthor | metal clusters | - |
dc.subject.keywordAuthor | X-ray structure | - |
dc.subject.keywordAuthor | mu-oxo complexes | - |
dc.subject.keywordAuthor | carbonyl | - |
dc.subject.keywordPlus | OSMIUM CARBONYL HYDRIDES | - |
dc.subject.keywordPlus | O BOND SCISSION | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | TRIOSMIUM CLUSTER | - |
dc.subject.keywordPlus | SOLUTION DYNAMICS | - |
dc.subject.keywordPlus | ACYL LIGAND | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | METAL | - |
dc.subject.keywordPlus | ALKYLIDENE | - |
dc.subject.keywordPlus | CPWOS3(CO)9(MU-O)(MU-3-CCH2TOL) | - |
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