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Metal atom lability in polynuclear complexes.

ABSTRACT: The asymmetric oxidation product [((Ph)L)Fe3(?-Cl)]2 [(Ph)LH6 = MeC(CH2NHPh-o-NHPh)3], where each trinuclear core is comprised of an oxidized diiron unit [Fe2](5+) and an isolated trigonal pyramidal ferrous site, reacts with MCl2 salts to afford heptanuclear bridged structures of the type ((Ph)L)2Fe6M(?-Cl)4(thf)2, where M = Fe or Co. Zero-field, (57)Fe Mössbauer analysis revealed the Co resides within the trinuclear core subunits, not at the octahedral, halide-bridged MCl4(thf)2 position indicating Co migration into the trinuclear subunits has occurred. Reaction of [((Ph)L)Fe3(?-Cl)]2 with CoCl2 (2 or 5 equivalents) followed by precipitation via addition of acetonitrile afforded trinuclear products where one or two irons, respectively, can be substituted within the trinuclear core. Metal atom substitution was verified by (1)H NMR, (57)Fe Mossbauer, single crystal X-ray diffraction, X-ray fluorescence, and magnetometry analysis. Spectroscopic analysis revealed that the Co atom(s) substitute(s) into the oxidized dimetal unit ([M2](5+)), while the M(2+) site remains iron-substituted. Magnetic data acquired for the series are consistent with this analysis revealing the oxidized dimetal unit comprises a strongly coupled S = 1 unit ([FeCo](5+)) or S = 1/2 ([Co2](5+)) that is weakly antiferromagnetically coupled to the high spin (S = 2) ferrous site. The kinetic pathway for metal substitution was probed via reaction of [((Ph)L)Fe3(?-Cl)]2 with isotopically enriched (57)FeCl2(thf)2, the results of which suggest rapid equilibration of (57)Fe into both the M(2+) site and oxidized diiron site, achieving a 1:1 mixture.

SUBMITTER: Eames EV

PROVIDER: S-EPMC3678548 | biostudies-literature | 2013 May

REPOSITORIES: biostudies-literature

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Metal atom lability in polynuclear complexes.

Eames Emily V EV Hernández Sánchez Raúl R Betley Theodore A TA

Inorganic chemistry 20130423 9

The asymmetric oxidation product [((Ph)L)Fe3(μ-Cl)]2 [(Ph)LH6 = MeC(CH2NHPh-o-NHPh)3], where each trinuclear core is comprised of an oxidized diiron unit [Fe2](5+) and an isolated trigonal pyramidal ferrous site, reacts with MCl2 salts to afford heptanuclear bridged structures of the type ((Ph)L)2Fe6M(μ-Cl)4(thf)2, where M = Fe or Co. Zero-field, (57)Fe Mössbauer analysis revealed the Co resides within the trinuclear core subunits, not at the octahedral, halide-bridged MCl4(thf)2 position indica ...[more]

PMID: 23642178

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Project description:Understanding the temporal effects of organic matter input and water influx on metal lability and translocation is critical to evaluate the success of the phytostabilization of metalliferous mine tailings. Trends of metal lability, e.g., V, Cr, Mn, Co, Ni, Cu, Zn, and Pb, were investigated for three years following a direct-planting phytostabilization trial at a Superfund mine tailings site in semi-arid central Arizona, USA. Unamended tailings were characterized by high concentrations (mmol kg-1) of Fe (2100), S (3100), As (41), Zn (39), and Pb (11), where As and Pb greatly exceeded non-residential soil remediation levels established by Arizona. Phytostabilization treatments included a no-compost control, 100 g kg-1 compost with seed, and 200 g kg-1 compost with and without seed to the top 20 cm of the tailings profile. All plots received supplemental irrigation, effectively doubling the mean annual precipitation. Tailings cores up to 90 cm were Collected at the time of planting and every summer for 3 years. The cores were sub-sectioned at 20 cm increments and analyzed via total digestion and an operationally defined sequential extraction for elemental analysis and the calculation of a mass transfer coefficient normalized to Ti as an assigned immobile element. The results indicate that Pb was recalcitrant and relatively immobile in the tailings environment for both the uncomposted control and composted treatments with a maximum variation in the total concentration of 9-14 mmol kg-1 among all samples. Metal lability and translocation above the redox boundary (ca. 30 cm depth) was governed by acid generation, where surficial pH was measured as low as 2.7 ± 0.1 in year three and strongly correlated with the increased lability of Mn, Co, Ni, Cu, and Zn. There was no significant pH effect on the lability of V, Cr, or Pb. Translocation to depths was greatest for Mn and Co; however, Zn, Ni, Cr, and Cu were also mobilized. The addition of organic matter enhanced the mobilization of Cr from the near surface to 40-60 cm depth (pH > 6) over the three-year phytostabilization study compared to the control. The increased enrichment of some metals at 60-90 cm indicates that the long-term monitoring of elemental translocation is necessary to assess the efficacy of phytostabilization to contain subsurface metal contaminants and thereby protect the surrounding community from exposure.

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Metal atom lability in polynuclear complexes.

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Metal atom lability in polynuclear complexes.

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