Substituent Effects on Nitrosyl Iron Corrole Complexes Fe(Ar<sub>3</sub>C)(NO)
Crisjoe A. Joseph
Matthew S. Lee
Alexei V. Iretskii
Guang Wu
Peter C. Ford
10.1021/ic051956j.s002
https://acs.figshare.com/articles/dataset/Substituent_Effects_on_Nitrosyl_Iron_Corrole_Complexes_Fe_Ar_sub_3_sub_C_NO_/3234862
A series of nitrosyl tris(5,10,15-aryl)corrolate complexes of iron(III) Fe(Ar<sub>3</sub>C)(NO) with different substituents on the
aryl groups have been prepared, and certain spectroscopic and reaction properties were compared. The cyclic
voltammetric analysis of the various Fe(Ar<sub>3</sub>C)(NO) complexes demonstrated that both the one-electron oxidation
and one-electron reduction potentials respond in systematic and nearly identical trends relative to the electron-donor properties of the substituents. A similar pattern was seen in the nitrosyl stretching frequency, ν<sub>NO</sub>, which
modestly decreased with the stronger donor substituents. Flash photolysis of Fe(Ar<sub>3</sub>C)(NO) solutions in toluene
leads to NO dissociation followed by rapid [NO]-dependent decay of the transients formed (presumably Fe(Ar<sub>3</sub>C))
to regenerate the original spectra. As was seen in an earlier flash photolysis study of Fe(TNPC)(NO) (TNPC<sup>3-</sup> =
5,10,15-tris(4-nitro-phenyl)corrolate; Joseph, C.; Ford, P. C. <i>J. Am. Chem. Soc</i>. <b>2005</b>, <i>127</i>, 6737−6743), the second-order rate constants, <i>k</i><sub>NO</sub>, are all much faster ((1−9) × 10<sup>8</sup> M<sup>-1</sup> s<sup>-1</sup> at 298 K) than those for analogous iron(III)
complexes of porphyrins. However, on a more microscopic level there is no obvious pattern in these rates with
respect to the donor properties of the aryl ring substituents. The high reactivity of the ferric triarylcorrolates with NO
data is interpreted in terms of the strongly electron-donating character of the Ar<sub>3</sub>C<sup>3-</sup> ligand and the quartet electronic
configuration of the Fe(Ar<sub>3</sub>C) intermediate.
2006-03-06 00:00:00
reaction properties
298 K
Flash photolysis
aryl ring substituents
donor properties
Substituent Effects
TNPC
aryl groups
rate constants
flash photolysis study
ferric triarylcorrolates
Fe
donor substituents
cyclic voltammetric analysis
complex