Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/744
Título: Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour
Autor: Dinoi, Chiara
Guedes da Silva, M. Fatima C.
Alegria, Elisabete Clara Bastos do Amaral
Smolenski, Piotr
Martins, Luísa Margarida D. R. S.
Poli, Rinaldo
Pombeiro, Armando J. L.
Palavras-chave: Molybdenum
Scorpionates
Electrochemistry
Solid-state structures
Data: Jun-2010
Editora: Wiley-Viley C H Verlag GMBH
Citação: Dinoi C, Silva M F C G, Alegria E C B A, Smolenski P, Martins L M D R S, Poli R, Pombeiro A J L. Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour. European Journal of Inorganic Chemistry. 2010; (16): 2415-2424.
Relatório da Série N.º: 16
Resumo: The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.
Peer review: yes
URI: http://hdl.handle.net/10400.21/744
ISSN: 1434-1948
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos



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