Spectroscopic properties and electronic structure of five- and six-coordinate iron(II) porphyrin NO complexes: Effect of the axial N-donor ligand.
In this paper, the differences in the spectroscopic properties and electronic structures of five- and six-coordinate iron(II) porphyrin NO complexes are explored using [Fe(TPP)(NO)] (1; TPP = tetraphenylporphyrin) and [Fe(TPP)(MI)(NO)] (2; MI = 1-methylimidazole) type systems. Binding of N-donor ligands in axial position trans to NO to five-coordinate complexes of type 1 is investigated using UV-vis absorption and 1H NMR spectroscopies. This way, the corresponding binding constants Keq are determined and the 1H NMR spectra of 1 and 2 are assigned for the first time. In addition, 1H NMR allows for the determination of the degree of denitrosylation in solutions of 1 with excess base. The influence of the axial ligand on the properties of the coordinated NO is then investigated. Vibrational spectra (IR and Raman) of 1 and 2 are presented and assigned using isotope substitution and normal-coordinate analysis. Obtained force constants are 12.53 (N-O) and 2.98 mdyn/A (Fe-NO) for 1 compared to 11.55 (N-O) and 2.55 mdyn/A (Fe-NO) for 2. Together with the NMR results, this provides experimental evidence that binding of the trans ligand weakens the Fe-NO bond. The principal bonding schemes of 1 and 2 are very similar. In both cases, the Fe-N-O subunit is strongly bent. Donation from the singly occupied pi* orbital of NO into d(z2) of iron(II) leads to the formation of an Fe-NO sigma bond. In addition, a medium-strong pi back-bond is present in these complexes. The most important difference in the electronic structures of 1 and 2 occurs for the Fe-NO sigma bond, which is distinctively stronger for 1 in agreement with the experimental force constants. The increased sigma donation from NO in 1 also leads to a significant transfer of spin density from NO to iron, as has been shown by magnetic circular dichroism (MCD) spectroscopy in a preceding Communication (Praneeth, V. K. K.; Neese, F.; Lehnert, N. Inorg. Chem. 2005, 44, 2570-2572). This is confirmed by the 1H NMR results presented here. Hence, further experimental and computational evidence is provided that complex 1 has noticeable Fe(I)NO+ character relative to 2, which is an Fe(II)NO(radical) complex. Finally, using MCD theory and quantum chemical calculations, the absorption and MCD C-term spectra of 1 and 2 are assigned for the first time.
Institut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Olshausenstrasse 40, D-24098 Kiel, Germany.
V K K
VK
Praneeth
Christian
C
Näther
Gerhard
G
Peters
Nicolai
N
Lehnert
D001665:Binding Sites; D018360:Crystallography, X-Ray; D004583:Electrons; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D014732:Vibration
D005296:Ferrous Compounds; D008024:Ligands; D011166:Porphyrins; D009569:Nitric Oxide