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See detailA Seven-Coordinate Iron Platform and its Oxo and Nitrene Reactivity
Soo, Han Sen; Sougrati, Moulay T; Grandjean, Fernande ULg et al

in Inorganica Chimica Acta (2011), 369

We present a new structurally determined seven-coordinate iron platform supported by the tris(2picolyl)amine ligand 6,60 -(pyridin-2-ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O ... [more ▼]

We present a new structurally determined seven-coordinate iron platform supported by the tris(2picolyl)amine ligand 6,60 -(pyridin-2-ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)–triflate complex [TPA 2C(O)NHtBuFeII(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) l-oxo complex [(TPA 2C(O)NHtBuFeIII) 2(O)][OTf]4 (5). Mossbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC6H4SO2) and PhINNs (Ns = p-NO2C6H4SO2) provide the corresponding iron(III)-amide congeners [TPA 2C(O)NHtBuFeIII(NHTs)][OTf]2 (6) and [TPA 2C(O)NHtBuFeIII(NHNs)][OTf] 2 (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal–ligand multiply bonded species supported by approximate pentagonal-type ligand fields. [less ▲]

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See detailZinc complexes with 1,2,4-triazole functionalized amino acid derivatives: Synthesis, structure and b-lactamase assay
Naik, Anil; Beck, Joséphine; Dîrtu, Marinela et al

in Inorganica Chimica Acta (2011), 368

Coordinating abilities of 4R-1,2,4-triazole derivatives (R = glycine ethyl ester (L1), glycine (L2), diethylamino malonate (L3), methionine (L4) and diethyl aminomethylphosphonate (L5)) towards ZnII ions ... [more ▼]

Coordinating abilities of 4R-1,2,4-triazole derivatives (R = glycine ethyl ester (L1), glycine (L2), diethylamino malonate (L3), methionine (L4) and diethyl aminomethylphosphonate (L5)) towards ZnII ions have been studied in solution, in solid state and versus three zinc-b-lactamases. The crystal structure of [Zn3(L4)6(H2O)6] (6) is described; it is the first crystal structure involving a 1,2,4-triazole functionalized methionine. It forms a trinuclear complex with central zinc octahedrally coordinated by only L4, whereas terminal zinc ions coordination sphere is completed by three water molecules. L4 exhibits a dual functionality of a bridging bidentate ligand as well as an anion. A dense hydrogen bonding network connects these trinuclear entity into a 3D supramolecular network. The ZnII ions in 6 are held at equidistance (3.848 Å) which coincidently matches with the corresponding Zn Zn distance in the binuclear zinc enzyme from Bacillus cereus (3.848 and 4.365 Å). Among L1–L5 screened for b-lactamase assay, L4 shows modest inhibition for BcII enzyme. [less ▲]

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