Metal Atom Lability in Polynuclear Complexes

DSpace/Manakin Repository

Metal Atom Lability in Polynuclear Complexes

Citable link to this page


Title: Metal Atom Lability in Polynuclear Complexes
Author: Eames, Emily V.; Hernandez sanchez, Raul; Betley, Theodore A

Note: Order does not necessarily reflect citation order of authors.

Citation: Eames, Emily V., Raúl Hernández Sánchez, and Theodore A. Betley. 2013. Metal Atom Lability in Polynuclear Complexes. Inorganic Chemistry 52, no. 9: 5006–5012.
Access Status: Full text of the requested work is not available in DASH at this time (“dark deposit”). For more information on dark deposits, see our FAQ.
Full Text & Related Files:
Abstract: The asymmetric oxidation product [(PhL)Fe3(μ-Cl)]2 [PhLH6 = 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 (PhL)2Fe6M(μ-Cl)4(thf)2, where M = Fe or Co. Zero-field, 57Fe 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 [(PhL)Fe3(μ-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 1H NMR, 57Fe 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 M2+ 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 [(PhL)Fe3(μ-Cl)]2 with isotopically enriched 57FeCl2(thf)2, the results of which suggest rapid equilibration of 57Fe into both the M2+ site and oxidized diiron site, achieving a 1:1 mixture.
Published Version: doi:10.1021/ic302694y
Other Sources:
Citable link to this page:
Downloads of this work:

Show full Dublin Core record

This item appears in the following Collection(s)


Search DASH

Advanced Search