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標題: Structure and dynamic behavior of CF(3)CO(2)(-) in solution with a previously unknown eta(2) chelation mode to silver(I) in Ag(2)(2-NCH(2)C(6)H(5)NCTPP)(2) (2+)center dot Ag(2)(O(2)CCF(3))(4) (2-)
作者: Hsaio, De-Zhi
Chen, Jyh-Horung
Wang, Shin-Shin
Tung, Jo-Yu
關鍵字: Windmill;Paddlewheel;X-ray diffraction;(19)F NMR;Silver(I,III);N-confused porphyrin;earth benzoate complexes;n-confused porphyrin;single-crystal;coordination;ligands
Project: Polyhedron, Volume 30, Issue 17, Page(s) 2908-2913.
Reaction of N-confused porphyrin 2 (2-NCH(2)C(6)H(5)NCTPPH) with silver(I) trifluoroacetate in CH(3)CN gave a good yield of the related silver(III) complex [Ag(2)(2-NCH(2)C(6)H(5)NCTPP)(2)](2+)center dot[Ag(2)(O(2)CCF(3))(4)](2-) (3). The oxidation state of the central metal in complex 3 was inferred from the diamagnetic NMR spectrum. The square-planar structure of this Ag(III) complex was elucidated by X-ray single-crystal analyses. X-ray diffraction analysis shows that the anion of complex 3, (3(A); [Ag(2)(O(2)CCF(3))(4)](2-)), contains two different bonding modes of the fluorocarboxylate to the Ag atoms, including the first example of the terminal bidentate eta(2) mode. The free energy of activation at the coalescence temperature T(c) and thermodynamic parameters for the isomerization process between the form I (windmill) isomer of 3(A), I(3(A)), and the form II (paddlewheel) isomer of 3(A), II(3(A)), in CD(2)Cl(2) solvent of the disilver compound is found to be Delta G(221)(not equal) = 9.29 kcal/mol and Delta H = -257 cal/mol, respectively, through (19)F NMR temperature-dependent measurements. (C) 2011 Elsevier Ltd. All rights reserved.
ISSN: 0277-5387
DOI: 10.1016/j.poly.2011.08.034
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