Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States.

An isostructural series of Fe, Fe, and Fe complexes [Fe(ImP)] utilizing the ImP 1,1'-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene) ligand, combining -heterocyclic carbenes and cyclometalating functions, is presented. The strong donor motif stabilizes the high-valent Fe oxidation state yet keeps the Fe oxidation state accessible from the parent Fe compound. Chemical oxidation of [Fe(ImP)] yields stable [Fe(ImP)].

Detection and Characterization of Hydride Ligands in Copper Complexes by Hard X-Ray Spectroscopy.

Transition metal complexes, particularly copper hydrides, play an important role in various catalytic processes and molecular inorganic chemistry. This study employs synchrotron hard X-ray spectroscopy to gain insights into the geometric and electronic properties of copper hydrides as potential catalysts for CO hydrogenation. The potential of high energy resolution X-ray absorption near-edge structure (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is demonstrated with measurement on Stryker's reagent (CuH) and [Cu(μ-H)(dpmppe)](PF) (CuH), alongside a non-hydride copper compound ICu(dtbppOH) (Cuy-I).

Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles.

The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe , Fe , and Fe nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.

When Donors Turn into Acceptors: Ground and Excited State Properties of Fe Complexes with Amine-Substituted Tridentate Bis-imidazole-2-ylidene Pyridine Ligands.

In search of new ligand motifs for photoactive iron(II) complexes with long-lived MLCT states, a series of six complexes with tridentate amine-functionalized bis--heterocyclic carbene (NHC)-pyridine ligands is presented. In the homoleptic complexes imidazole-, methylimidazole-, or benzimidazole-2-ylidene, NHC donors are employed in combination with pyridine, functionalized in the 4-position by dimethylamine or dibenzylamine. The effects of these different functionalities on the electronic structure of the complexes are examined through detailed ground state characterization by NMR, single crystal X-ray diffraction, as well as electrochemical and spectroscopic methods.

Stereoselective Alkyne Hydrogenation by using a Simple Iron Catalyst.

The stereoselective hydrogenation of alkynes constitutes one of the key approaches for the construction of stereodefined alkenes. The majority of conventional methods utilize noble and toxic metal catalysts. This study concerns a simple catalyst comprised of the commercial chemicals iron(II) acetylacetonate and diisobutylaluminum hydride, which enables the Z-selective semihydrogenation of alkynes under near ambient conditions (1-3 bar H , 30 °C, 5 mol % [Fe]).