Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)

Glaser T, Kesting F, Beissel T, Bill E, Weyhermuller T, Meyer-Klaucke W, Wieghardt K (1999)
Inorganic Chemistry 38(4): 722-732.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Autor*in
Glaser, ThorstenUniBi; Kesting, F; Beissel, T; Bill, E; Weyhermuller, T; Meyer-Klaucke, W; Wieghardt, K
Abstract / Bemerkung
The reaction of mononuclear [LFe(III)] where L represents the trianionic ligand 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane with NiCl(2). 6H(2)O and subsequent oxidations with [Ni(III)(tacn)(2)](ClO(4))(3) (tacn = 1,4,7-triazacyclononane) and PbO(2)/methanesulfonic acid produced an isostructural series of complexes [LFeNiFeL](n+) (n = 2 (1), n = 3 (2), n = 4 (3)), which were isolated as PF(6)(-) (1, 3) or ClO(4)(-) salts (2). The molecular structures were established by X-ray crystallography for [LFeNiFeL](ClO(4))(2). 5CH(3)CN (1*), C(88)H(123)Cl(2)Fe(2)N(11)NiO(8)S(6), and [LFeNiFeL](ClO(4))(3). 8acetone (2*), C(102)H(156)Cl(3)Fe(2)N(6)NiO(20)S(6). Both compounds crystallize in the triclinic space group P (1) over bar with a = 13.065(2) Angstrom (13.155(2) Angstrom), b = 13.626(3) Angstrom (13.747(3) Angstrom), c = 14.043(3) Angstrom (16.237(3) Angstrom), alpha = 114.47(3)degrees (114.20(2)degrees), beta = 97.67(3)degrees (96.57(2)degrees), gamma = 90.34(3)degrees (98.86(2)degrees), Z = 1(1) (values in parentheses refer to 2*). The cations in 1, 2, and 3 have been determined to be isostructural by Fe and Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. All compounds contain linear trinuclear cations (face-sharing octahedral) with an N(3)Fe(mu-SR)(3)Ni(mu-SR)(3)FeN(3) core structure. The electronic structures of 1, 2, and 3 have been studied by Fe and Ni K-edge X-ray absorption near edge (XANES), UV-vis, EPR, and Mossbauer spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Complexes 1 and 3 possess an S(t) = 0 whereas 2 has an S(t) = 1/2 ground state. It is shown that the electronic structures cannot be described by using localized valences (oxidation states). Delocalized models invoking the double-exchange mechanism are appropriate; i.e., spin-dependent delocalization via a double-exchange mechanism yields the correct ground state in each case, 1, 2, and 3 represent the first examples where double exchange stabilizes a ground state of minimum spin multiplicity.
Erscheinungsjahr
1999
Zeitschriftentitel
Inorganic Chemistry
Band
38
Ausgabe
4
Seite(n)
722-732
ISSN
0020-1669
eISSN
1520-510X
Page URI
https://pub.uni-bielefeld.de/record/2398102

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Glaser T, Kesting F, Beissel T, et al. Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry. 1999;38(4):722-732.
Glaser, T., Kesting, F., Beissel, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., & Wieghardt, K. (1999). Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry, 38(4), 722-732. https://doi.org/10.1021/ic9811289
Glaser, Thorsten, Kesting, F, Beissel, T, Bill, E, Weyhermuller, T, Meyer-Klaucke, W, and Wieghardt, K. 1999. “Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)”. Inorganic Chemistry 38 (4): 722-732.
Glaser, T., Kesting, F., Beissel, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., and Wieghardt, K. (1999). Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry 38, 722-732.
Glaser, T., et al., 1999. Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry, 38(4), p 722-732.
T. Glaser, et al., “Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)”, Inorganic Chemistry, vol. 38, 1999, pp. 722-732.
Glaser, T., Kesting, F., Beissel, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., Wieghardt, K.: Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry. 38, 722-732 (1999).
Glaser, Thorsten, Kesting, F, Beissel, T, Bill, E, Weyhermuller, T, Meyer-Klaucke, W, and Wieghardt, K. “Spin-dependent delocalization in three isostructural complexes [LFeNiFeL](2+/3+/4+) (L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)”. Inorganic Chemistry 38.4 (1999): 722-732.

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PMID: 29446427
Valence Interconversion of Octahedral Nickel(II/III/IV) Centers.
Kouno M, Yoshinari N, Kuwamura N, Yamagami K, Sekiyama A, Okumura M, Konno T., Angew Chem Int Ed Engl 56(44), 2017
PMID: 28846211
Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes.
Wang Y, Lin C, Ma X, Xue Z, Zhu X, Cao W, Hu S, Sheng T, Wu X., Dalton Trans 44(16), 2015
PMID: 25801952
Synthesis of open-shell, bimetallic Mn/Fe trinuclear clusters.
Powers TM, Gu NX, Fout AR, Baldwin AM, Hernández Sánchez R, Alfonso DM, Chen YS, Zheng SL, Betley TA., J Am Chem Soc 135(38), 2013
PMID: 23984911
Redox non-innocence of thioether crowns: spectroelectrochemistry and electronic structure of formal nickel(III) complexes of aza-thioether macrocycles.
Stephen E, Huang D, Shaw JL, Blake AJ, Collison D, Davies ES, Edge R, Howard JA, McInnes EJ, Wilson C, Wolowska J, McMaster J, Schröder M., Chemistry 17(37), 2011
PMID: 21837715
Ferromagnetic nanoscale electron correlation promoted by organic spin-dependent delocalization.
Kirk ML, Shultz DA, Schmidt RD, Habel-Rodriguez D, Lee H, Lee J., J Am Chem Soc 131(51), 2009
PMID: 19928960
Molecular and electronic structures of one-electron oxidized Ni(II)-(dithiosalicylidenediamine) complexes: Ni(III)-thiolate versus Ni(II)-thiyl radical states.
Stenson PA, Board A, Marin-Becerra A, Blake AJ, Davies ES, Wilson C, McMaster J, Schröder M., Chemistry 14(8), 2008
PMID: 18213560
Ferro- and antiferromagnetic interactions in face-sharing trioctahedral Ni(II)Mn(II)Ni(II) and Ni(II)Fe(III)Ni(II) complexes with the same 1-5/2-1 spin system.
Kobayashi T, Yamaguchi T, Ohta H, Sunatsuki Y, Kojima M, Re N, Nonoyama M, Matsumoto N., Chem Commun (Camb) (18), 2006
PMID: 16767246
Modulation of the electronic structure and the Ni-Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase.
Zhu W, Marr AC, Wang Q, Neese F, Spencer DJ, Blake AJ, Cooke PA, Wilson C, Schröder M., Proc Natl Acad Sci U S A 102(51), 2005
PMID: 16352727
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