TY - JOUR
T1 - Oxidation and reduction of bis(imino)pyridine iron dinitrogen complexes
T2 - Evidence for formation of a chelate trianion.
AU - Tondreau, Aaron M.
AU - Stieber, S. Chantal E.
AU - Milsmann, Carsten
AU - Lobkovsky, Emil
AU - Weyhermüller, Thomas
AU - Semproni, Scott P.
AU - Chirik, Paul J.
PY - 2013/1/18
Y1 - 2013/1/18
N2 - Oxidation and reduction of the bis(imino)pyridine iron dinitrogen compound, (iPrPDI)FeN2 (iPrPDI = 2,6-(2,6- iPr2-C6H3-N=CMe)2C 5H3N) has been examined to determine whether the redox events are metal or ligand based. Treatment of (iPrPDI)FeN 2 with [Cp2Fe][BArF4] (BAr F4 = B(3,5-(CF3)2-C 6H3)4) in diethyl ether solution resulted in N2 loss and isolation of [(iPrPDI)Fe(OEt 2)][BArF4]. The electronic structure of the compound was studied by SQUID magnetometry, X-ray diffraction, EPR and zero-field 57Fe Mössbauer spectroscopy. These data, supported by computational studies, established that the overall quartet ground state arises from a high spin iron(II) center (SFe = 2) antiferromagnetically coupled to a bis(imino)pyridine radical anion (SPDI = 1/2). Thus, the oxidation event is principally ligand based. The one electron reduction product, [Na(15-crown-5)][(iPrPDI)FeN2], was isolated following addition of sodium naphthalenide to (iPrPDI)FeN2 in THF followed by treatment with the crown ether. Magnetic, spectroscopic, and computational studies established a doublet ground state with a principally iron-centered SOMO arising from an intermediate spin iron center and a rare example of trianionic bis(imino)pyridine chelate. Reduction of the iron dinitrogen complex where the imine methyl groups have been replaced by phenyl substituents, (iPrBPDI)Fe(N2)2 resulted in isolation of both the mono-and dianionic iron dinitrogen compounds, [( iPrBPDI)FeN2]- and [(iPrBPDI) FeN2]2-, highlighting the ability of this class of chelate to serve as an effective electron reservoir to support neutral ligand complexes over four redox states.
AB - Oxidation and reduction of the bis(imino)pyridine iron dinitrogen compound, (iPrPDI)FeN2 (iPrPDI = 2,6-(2,6- iPr2-C6H3-N=CMe)2C 5H3N) has been examined to determine whether the redox events are metal or ligand based. Treatment of (iPrPDI)FeN 2 with [Cp2Fe][BArF4] (BAr F4 = B(3,5-(CF3)2-C 6H3)4) in diethyl ether solution resulted in N2 loss and isolation of [(iPrPDI)Fe(OEt 2)][BArF4]. The electronic structure of the compound was studied by SQUID magnetometry, X-ray diffraction, EPR and zero-field 57Fe Mössbauer spectroscopy. These data, supported by computational studies, established that the overall quartet ground state arises from a high spin iron(II) center (SFe = 2) antiferromagnetically coupled to a bis(imino)pyridine radical anion (SPDI = 1/2). Thus, the oxidation event is principally ligand based. The one electron reduction product, [Na(15-crown-5)][(iPrPDI)FeN2], was isolated following addition of sodium naphthalenide to (iPrPDI)FeN2 in THF followed by treatment with the crown ether. Magnetic, spectroscopic, and computational studies established a doublet ground state with a principally iron-centered SOMO arising from an intermediate spin iron center and a rare example of trianionic bis(imino)pyridine chelate. Reduction of the iron dinitrogen complex where the imine methyl groups have been replaced by phenyl substituents, (iPrBPDI)Fe(N2)2 resulted in isolation of both the mono-and dianionic iron dinitrogen compounds, [( iPrBPDI)FeN2]- and [(iPrBPDI) FeN2]2-, highlighting the ability of this class of chelate to serve as an effective electron reservoir to support neutral ligand complexes over four redox states.
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U2 - 10.1021/ic301675t
DO - 10.1021/ic301675t
M3 - Article
C2 - 23268722
AN - SCOPUS:84872554580
SN - 0020-1669
VL - 52
SP - 635
EP - 646
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -