New pyridyl-pyrazinyl ketones as ligands for Cu(II), Ag(I), Zn(II) and Cd(II) complexes: Anion-dependent hydrolysis of 2,2 '-pyridyl-pyrazinyl ketone and unvaried neat forms of its positional isomers
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AbstractA series of Cu(II), Ag(I), Zn(II) and Cd(II) complexes of new pyridyl-pyrazinyl ketones 2-pyridinyl-2-pyrazinylmethanone (abbreviated as L1), 3-pyridinyl-2-pyrazinylmethanone (L2) and 4-pyridinyl-2-pyrazinylmethanone (L3) has been synthesized and characterized by single crystal X-ray analysis. L1 can takes not only its neat ketone form in [Ag(L1)(NO2)](infinity) (1), but also the gem-diol form (L1(a)) in [Ag(L1(a))(CF3CO2)](infinity) (2) and [Cu(L1(a))(2)](BF4)(2)center dot 4H(2)O (3) via in-situ metal-promoted nucleophilic reaction. L2 and L3 preferentially adopt their ketone forms in zinc(II) and cadmium(II) complexes [Zn(L2)(2)Cl-2] (4), [Cd(L2)(2)(NO3)(2)(H2O)(2)] (5), {[Cd(L2)(2)(H2O)(2)](BF4)(2)center dot 4H(2)O}(infinity) (6), {[Cd(L2)(2)(H2O)(2)](ClO4)(2)center dot 4H(2)O}(infinity) (7), [Cd(L3)(2)(H2O)(4)](NO3)(2) (8) and {[Cd-4(L3)(4)(ClO4)(2)](ClO4)(6)center dot 13H(2)O}(infinity) (9). The ligand behavior of L1-L3 incomplexes 1-9 are compared to that of di-2-pyridinylmethanone and its positional isomers. The metal-promoted nucleophilic reaction mechanism involving the carbonyl group in coordination complexes of the pyridyl ketone family is probed and discussed. Supramolecular architectures of complexes 1-9 with the various ketones are also observed and discussed. (C) 2015 Elsevier B.V. All rights reserved.
All Author(s) ListWan CQ, Yan HJ, Mak TCW
Journal nameInorganica Chimica Acta,Inorganica Chimica Acta
Volume Number432
Pages13 - 24
LanguagesEnglish-United Kingdom
KeywordsDipyridyl ketone; Metal complex; Metal-promoted reaction; Positional isomer; Supramolecular architecture
Web of Science Subject CategoriesChemistry; Chemistry, Inorganic & Nuclear

Last updated on 2021-25-01 at 02:22