Multimetallic Cooperativity in Activation of Dinitrogen at Iron-Potassium Sites.

The reaction of soluble iron-oxygen-potassium assemblies with N2 gives insight into the mechanisms of multimetallic N2 coordination. We report a series of very electron-rich three-coordinate, ß-diketiminate-supported iron(I) phenoxide complexes, which are metastable but have been characterized under Ar by both crystallography and solution methods. Both monomeric and dimeric Fe-OPh-K compounds have been characterized, and their iron environments are very similar in the solid and solution states. In the dimer, potassium ions hold together the phenoxide oxygens and aryl rings of the two halves, to give a flexible diiron core. The reactions of the monomeric and dimeric iron(I) compounds with N2 are surprisingly different: the mononuclear iron(I) complexes give no reaction with N2, but the dimeric Fe2K2 complex reacts rapidly to give a diiron-N2 product. Computational studies show that the key to the rapid N2 reaction of the dimer is the preorganization of the two iron atoms. Thus, cooperation between Fe (which weakens the N-N bond) and K (which orients the Fe atoms) can be used to create a low-energy pathway for N2 reactions.

Sensitivity of X-ray core spectroscopy to changes in metal ligation: a systematic study of low-coordinate, high-spin ferrous complexes.

In order to assess the sensitivity and complementarity of X-ray absorption and emission spectroscopies for determining changes in the metal ligation sphere, a systematic experimental and theoretical study of iron model complexes has been carried out. A series of high-spin ferrous complexes, in which the ligation sphere has been varied from a three-coordinate complex, [L(tBu)Fe(SPh)] (1) (where L(tBu) = bulky ß-diketiminate ligand; SPh = phenyl thiolate) to four-coordinate complexes [L(tBu)Fe(SPh)(X)] (where X = CN(t)Bu (2); 1-methylimidazole (3); or N,N-dimethylformamide (DMF) (4)), has been investigated using a combination of Fe K-edge X-ray absorption (XAS) and Kß X-ray emission (XES) spectroscopies. The Fe K XAS pre-edge and edge of all four complexes are consistent with a high-spin ferrous assignment, with the largest differences in the pre-edge intensities attributed to changes in covalency of the fourth coordination site. The X-ray emission spectra show pronounced changes in the valence to core region (V2C) as the identity of the coordinated ligand is varied. The experimental results have been correlated to density functional theory (DFT) calculations, to understand key molecular orbital contributions to the observed absorption and emission features. The calculations also have been extended to a series of hypothetical high-spin iron complexes to understand the sensitivity of XAS and XES techniques to different ligand protonation states ([L(tBu)Fe(II)(SPh)(NHn)](3-n) (n = 3, 2, 1, 0)), metal oxidation states [L(tBu)Fe(SPh)(N)](n-) (n = 3, 2, 1), and changes in the ligand identity [L(tBu)Fe(IV)(SPh)(X)](n-) (X = C(4-), N(3-), O(2-); n = 2, 1, 0). This study demonstrates that XAS pre-edge data have greater sensitivity to changes in oxidation state, while valence to core (V2C) XES data provide a more sensitive probe of ligand identity and protonation state. The combination of multiple X-ray spectroscopic methods with DFT results thus has the potential to provide for detailed characterization of complex inorganic systems in both chemical and biological catalysis.

Identification of a single light atom within a multinuclear metal cluster using valence-to-core X-ray emission spectroscopy.

Iron valence-to-core Fe Kß X-ray emission spectroscopy (V2C XES) is established as a means to identify light atoms (C, N, O) within complex multimetallic frameworks. The ability to distinguish light atoms, particularly in the presence of heavier atoms, is a well-known limitation of both crystallography and EXAFS. Using the sensitivity of V2C XES to the ionization potential of the bound ligand, energetic shifts of ~10 eV in the ligand 2s ionization energies of bound C, N, and O may be observed. As V2C XES is a high-energy X-ray method, it is readily applicable to samples in any physical form. This method thus has great potential for application to multimetallic inorganic frameworks involved in both small molecule storage and activation.

Ligand dependence of binding to three-coordinate Fe(II) complexes.

A series of three- and four-coordinate iron(II) complexes with nitrogen, chlorine, oxygen, and sulfur ligands is presented. The electronic variation is explored by measuring the association constant of the neutral ligands and the reduction potential of the iron(II) complexes. Varying the neutral ligand gives large changes in K(eq), which decrease in the order CN(t)Bu > pyridine >2-picoline > DMF > MeCN > THF > PPh(3). These differences can be attributed to a mixture of steric effects and electronic effects (both sigma-donation and pi-backbonding). The binding constants and the reduction potentials are surprisingly insensitive to changes in an anionic spectator ligand. This suggests that three-coordinate iron(II) complexes may have similar binding trends as proposed three-coordinate iron(II) intermediates in the FeMoco of nitrogenase, even though the anionic spectator ligands in the synthetic complexes differ from the sulfides in the FeMoco.

Synthesis of a bulky bis(imino)pyridine compound: a methodology for systematic variation of steric bulk and energetic implications for metalation.

A new bis(imino)pyridine compound, 2,6-{(2,6-Me(2)-C(6)H(3))NC(t-Bu)}(2)C(5)H(3)N (), has been synthesized with t-butyl substituents on the imino carbon atoms. The stepwise synthetic method for assembly of this compound is novel. Compound and its synthetic precursor, mono(imino)pyridine , have been characterized using single-crystal X-ray diffraction. Metalation attempts of using iron(ii) chloride under forcing conditions does not yield the desired iron(ii) chloride complex; the use of refluxing acetic acid solvent provides a minimal amount of a paramagnetic species that has been characterized by NMR spectroscopy and magnetic susceptibility (NMR method). Computational methods have been used to evaluate the relative energies of three conformations of bis(imino)pyridine ligands with varying alkyl substitution at the imino carbon positions. The relative energies of these closed, open and open-planar conformations of reveal a thermodynamic argument for the difficulty in metalation of , as compared to related ligands with less steric hindrance at the imino carbon atoms.