TY - JOUR
T1 - Reduction chemistry of aryl- and alkyl-substituted bis(imino)pyridine iron dihalide compounds
T2 - Molecular and electronic structures of [(PDI)2Fe] derivatives
AU - Wile, Bradley M.
AU - Trovitch, Ryan J.
AU - Bart, Suzanne C.
AU - Tondreau, Aaron M.
AU - Lobkovsky, Emil
AU - Milsmann, Carsten
AU - Bill, Eckhard
AU - Wieghardt, Karl
AU - Chink, Paul J.
PY - 2009/5/4
Y1 - 2009/5/4
N2 - Sodium amalgam reduction of the aryl-substituted bis(imino)pyridine iron dibromide complex, (EtPDI)FeBr2 (EtPDI = 2,6-(2,6-Et2-C6H3N=CMe)2C5H3N), under a dinitrogen atmosphere in pentane furnished the bis(chelate)iron compound, (EtPDI)2Fe. Characterization by X-ray crystallography established a distorted four-coordinate iron center with two K2-bis(imino)pyridine ligands. Reducing the steric demands of the imine substituent to either a less sterically encumbered aryl ring (e.g., C6H4-4-OMe) or an alkyl group (e.g., Cy, Pr, c/s-myrtanyl) also yielded bis(chelate) compounds from sodium amalgam reduction of the corresponding dihalide. Characterization of the compounds with smaller imine substituents by X-ray diffraction established six-coordinate, pseudo-octahedral compounds. In one case, a neutral bis(chelate)iron compound was prepared by reduction of the corresponding iron dication, [(PDI)2Fe]2+, providing chemical confirmation of electrochemically generated species that were previously reported as too reducing to isolate. Magnetic measurements, metrical parameters from X-ray structures, Mossbauer spectroscopy, and open-shell, broken symmetry DFT calculations were used to establish the electronic structure of both types (four- and six-coordinate) of neutral bis(chelate) compounds. The experimentally observed S = 1 compounds are best described as having high-spin ferrous (SFe = 2) centers antiferromagnetically coupled to two bis(imino)pyridine radical anions. Thus, the two-electron reduction of the diamagnetic, low-spin complex [(PDI)2Fe]2+ to [(PDI)2Fe] is ligand-based with a concomitant spin change at iron.
AB - Sodium amalgam reduction of the aryl-substituted bis(imino)pyridine iron dibromide complex, (EtPDI)FeBr2 (EtPDI = 2,6-(2,6-Et2-C6H3N=CMe)2C5H3N), under a dinitrogen atmosphere in pentane furnished the bis(chelate)iron compound, (EtPDI)2Fe. Characterization by X-ray crystallography established a distorted four-coordinate iron center with two K2-bis(imino)pyridine ligands. Reducing the steric demands of the imine substituent to either a less sterically encumbered aryl ring (e.g., C6H4-4-OMe) or an alkyl group (e.g., Cy, Pr, c/s-myrtanyl) also yielded bis(chelate) compounds from sodium amalgam reduction of the corresponding dihalide. Characterization of the compounds with smaller imine substituents by X-ray diffraction established six-coordinate, pseudo-octahedral compounds. In one case, a neutral bis(chelate)iron compound was prepared by reduction of the corresponding iron dication, [(PDI)2Fe]2+, providing chemical confirmation of electrochemically generated species that were previously reported as too reducing to isolate. Magnetic measurements, metrical parameters from X-ray structures, Mossbauer spectroscopy, and open-shell, broken symmetry DFT calculations were used to establish the electronic structure of both types (four- and six-coordinate) of neutral bis(chelate) compounds. The experimentally observed S = 1 compounds are best described as having high-spin ferrous (SFe = 2) centers antiferromagnetically coupled to two bis(imino)pyridine radical anions. Thus, the two-electron reduction of the diamagnetic, low-spin complex [(PDI)2Fe]2+ to [(PDI)2Fe] is ligand-based with a concomitant spin change at iron.
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U2 - 10.1021/ic801623m
DO - 10.1021/ic801623m
M3 - Article
C2 - 19035761
AN - SCOPUS:66149108466
SN - 0020-1669
VL - 48
SP - 4190
EP - 4200
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 9
ER -