Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/71131
標題: Thallium complexes of tetraphenylporphyrin: Tl(tpp-N-O)(OAc) and cis-acetato-N-p-tert-butylbenzensulfonylimido-meso-tetraphenylporphyrina tothallium(III) Tl(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(OAc)
作者: Yang, F.A.
Cho, K.Y.
Chen, J.H.
Wang, S.S.
Tung, J.Y.
Hsieh, H.Y.
Liao, F.L.
Lee, G.H.
Hwang, L.P.
Elango, S.
關鍵字: thallium
X-ray diffraction
N-oxide
torsion angle
dynamic NMR
metal-complexes
molecular-structure
group electronegativity
porphyrin
nickel(ii)
oxide
bond
期刊/報告no:: Polyhedron, Volume 25, Issue 11, Page(s) 2207-2214.
摘要: The crystal structures of Tl(tpp-N-O)(OAc) (3) and acetato-N-p-tert-butylbenzensulfonylimido-meso-tetraphenylporphyrinatothallium(III) Tl(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(OAc) (5) have been determined. The coordination sphere around Tl3+ is a distorted square-based pyramid in which the apical site is occupied by a bidentate chelating OAc- group for 3 and 5. The plane of three pyrrole nitrogen atoms (i.e., N(1), N(2) and N(3)), strongly bonded to Tl3+ in 3 and 5, is adopted as a reference plane, 3N. The porphyrin ring is severely distorted and the pyrrole ring N(4) bonding to the oxygen and (NSO2C6H4Bu)-Bu-t group makes a dihedral angle of 46.5 degrees and 46.7 degrees with the 3N plane for 3 and 5, respectively. In 3, Tl3+ and O(1) are located on the same side at 1.11 and 1.34 angstrom from its 3N plane, and in 5, Tl3+ and N(5) are also located on the same side at 1.15 and 1.30 angstrom from its 3N plane. The free energy of activation at the coalescence T-c for the intermolecular acetate exchange process of 3 and 5 in CD2Cl2 is found to be Delta G(184)double dagger = 39.3 and Delta G(208)double dagger = 44.1 kJ/mol, respectively, through H-1 NMR variable temperature measurements. An electronegative substituent, O(1), bonded to Tl in 3 causes a significant negative contribution up to 145 Hz for Delta(3)J(Tl-C, O) and 79 Hz for Delta(2) J(Tl-C, O) for OAc- in 3. (C) 2006 Elsevier Ltd. All rights reserved.
URI: http://hdl.handle.net/11455/71131
ISSN: 0277-5387
文章連結: http://dx.doi.org/10.1016/j.poly.2006.01.020
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