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Light-harvesting and intramolecular energy funneling are fundamental processes in natural photosynthesis. A comprehensive knowledge of the main structural, dynamic, and optical properties that regu...

In this issue of Chem Catalysis, de Ruiter and co-workers report a highly efficient and selective method for isomerization of a wide variety of terminal alkenes, employing the well-defined anionic complex [(PCNHCP)Fe(H)N2][Na]. This work also includes important insights about the structure and reactivity of the iron intermediates involved in the catalytic cycle.

Homoleptic iron-alkyl complexes have been implicated as key intermediates in iron-catalyzed cross-coupling with simple iron salts. Tetraalkyliron(III) ferrate species have been shown to be accessible with either methyl or benzyl ligands, where the former complex is S = 3/2 and distorted square planar while the latter is a S = 5/2 distorted tetrahedral species. In the current study, a new tetraalkyliron(III) complex is synthesized containing modified methylene substituents that incorporate large trimethylsilyl (TMS) groups to further probe steric and electronic ligand effects in tetraalkyliron(III) complexes by increasing the electron-donating ability of the ligand while retaining steric bulk. Detailed structural and DFT studies provide insight into electronic structure and bonding of the four-coordinate trimethylsilylmethyl iron(III) complex compared to the previously reported analogs containing methyl and benzyl ligands.