Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/69274
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dc.contributor.authorChen, K.T.en_US
dc.contributor.authorTsai, M.Y.en_US
dc.contributor.authorChen, J.H.en_US
dc.contributor.authorWang, S.S.en_US
dc.contributor.authorTung, J.Y.en_US
dc.date2010zh_TW
dc.date.accessioned2014-06-11T05:58:05Z-
dc.date.available2014-06-11T05:58:05Z-
dc.identifier.issn1387-7003zh_TW
dc.identifier.urihttp://hdl.handle.net/11455/69274-
dc.description.abstractThe crystal structures of diamagnetic (cis-acetato) (N-o-chlorobenzamido-meso-tetraphenylporphyrinato)thallium(III)center dot 0.5 water solvate [cis-Tl(N-NCO(o-Cl)C6H4-tpp)(OAc)center dot 0.5 H2O; 3 center dot 0.5 H2O] and diamagnetic (trans-acetato) (N-o-chlorobenzamido-meso-tetraphenylporphyrinato)cadmium(II) methylene chloride solvate [trans-Cd(N-NHCO(o-Cl)C(6)H(4)APP)(OAc)center dot CH2Cl2; 4 center dot CH2Cl2] were determined. The coordination sphere around the Tl3+ (or Cd2+) in 3 (or 4) is a distorted square-based pyramid in which the apical site is occupied by a chelating bidentate OAc- group. In 3, Tl3+ and N(5) are located on the same side at 1.18 and 1.26 angstrom from it 3N plane, but in 4, Cd2+ and N(5) are located on different sides at 1.06 and -1.55 angstrom from it 3N plane. The free energy of activation at the coalescence temperature T-c for the intermolecular acetate exchange process in 3 in CD2Cl2 solvent is found to be Delta G(198)(not equal) = 42.1 kJ/mol through H-1 NMR temperature-dependent measurements. Likewise, the free energy of activation = 55.94 kJ/mol is determined for the intramolecular exchange of the ortho protons between o'-H (34, 40) and o'-H (38, 44) in 3 in CD2Cl2. VT NMR (H-1 and C-13) studies of 4 show that the acetate acts as a bidentate ligand and the OAc- exchange does not occur in CD2Cl2. Moreover, the NH proton [i.e., H(5)] of 4 in CD2Cl2 is observed as a singlet at delta -0.09 ppm with Delta v(1/2) = 13 Hz at 20 degrees C indicating that the NH protons undergo intermediate intermolecular proton exchange with water at this temperature. (c) 2010 Elsevier B.V. All rights reserved.en_US
dc.language.isoen_USzh_TW
dc.relationInorganic Chemistry Communicationsen_US
dc.relation.ispartofseriesInorganic Chemistry Communications, Volume 13, Issue 4, Page(s) 506-510.en_US
dc.relation.urihttp://dx.doi.org/10.1016/j.inoche.2010.01.022en_US
dc.subjectThalliumen_US
dc.subjectCadmiumen_US
dc.subjectX-ray diffractionen_US
dc.subjectN-Substituted-N-aminoporphyrinen_US
dc.subjectDynamic NMRen_US
dc.subjectvalence statesen_US
dc.subjectelectronegativitiesen_US
dc.subjectelementsen_US
dc.subjectsolvateen_US
dc.titleMetal complexes of N-o-chlorobenzamido-meso-tetraphenylporphyrin: cis-Tl(N-NCO(o-Cl)C6H4-tpp)(OAc) and trans-Cd(N-NHCO(o-Cl)C6H4-tpp)(OAc) (tpp=5, 10, 15, 20-tetraphenylporphyrinate)en_US
dc.typeJournal Articlezh_TW
dc.identifier.doi10.1016/j.inoche.2010.01.022zh_TW
item.grantfulltextnone-
item.openairetypeJournal Article-
item.languageiso639-1en_US-
item.fulltextno fulltext-
item.cerifentitytypePublications-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
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