Development and Evolution of Mechanistic Understanding in Iron-Catalyzed Cross-Coupling.

Since the pioneering work of Kochi in the 1970s, iron has attracted great interest for cross-coupling catalysis due to its low cost and toxicity as well as its potential for novel reactivity compared to analogous reactions with precious metals like palladium. Today there are numerous iron-based cross-coupling methodologies available, including challenging alkyl-alkyl and enantioselective methods. Furthermore, cross-couplings with simple ferric salts and additives like NMP and TMEDA ( N-methylpyrrolidone and tetramethylethylenediamine) continue to attract interest in pharmaceutical applications. Despite the tremendous advances in iron cross-coupling methodologies, in situ formed and reactive iron species and the underlying mechanisms of catalysis remain poorly understood in many cases, inhibiting mechanism-driven methodology development in this field. This lack of mechanism-driven development has been due, in part, to the challenges of applying traditional characterization methods such as nuclear magnetic resonance (NMR) spectroscopy to iron chemistry due to the multitude of paramagnetic species that can form in situ. The application of a broad array of inorganic spectroscopic methods (e.g., electron paramagnetic resonance, 57Fe Mössbauer, and magnetic circular dichroism) removes this barrier and has revolutionized our ability to evaluate iron speciation. In conjunction with inorganic syntheses of unstable organoiron intermediates and combined inorganic spectroscopy/gas chromatography studies to evaluate in situ iron reactivity, this approach has dramatically evolved our understanding of in situ iron speciation, reactivity, and mechanisms in iron-catalyzed cross-coupling over the past 5 years. This Account focuses on the key advances made in obtaining mechanistic insight in iron-catalyzed carbon-carbon cross-couplings using simple ferric salts, iron-bisphosphines, and iron- N-heterocyclic carbenes (NHCs). Our studies of ferric salt catalysis have resulted in the isolation of an unprecedented iron-methyl cluster, allowing us to identify a novel reaction pathway and solve a decades-old mystery in iron chemistry. NMP has also been identified as a key to accessing more stable intermediates in reactions containing nucleophiles with and without ß-hydrogens. In iron-bisphosphine chemistry, we have identified several series of transmetalated iron(II)-bisphosphine complexes containing mesityl, phenyl, and alkynyl nucleophile-derived ligands, where mesityl systems were found to be unreliable analogues to phenyls. Finally, in iron-NHC cross-coupling, unique chelation effects were observed in cases where nucleophile-derived ligands contained coordinating functional groups. As with the bisphosphine case, high-spin iron(II) complexes were shown to be reactive and selective in cross-coupling. Overall, these studies have demonstrated key aspects of iron cross-coupling and the utility of detailed speciation and mechanistic studies for the rational improvement and development of iron cross-coupling methods.

Backbone Dehydrogenation in Pyrrole-Based Pincer Ligands.

Treatment of both [CoCl( tBuPNP)] and [NiCl( tBuPNP)] ( tBuPNP = anion of 2,5-bis((di- tert-butylphosphino)methyl)pyrrole) with one equivalent of benzoquinone affords the corresponding chloride complexes containing a dehydrogenated PNP ligand, tBudPNP ( tBudPNP = anion of 2,5-bis((di- tert-butylphosphino)methylene)-2,5-dihydropyrrole). Dehydrogenation of PNP to dPNP results in minimal change to steric profile of the ligand but has important consequences for the resulting redox potentials of the metal complexes, resulting in the ability to isolate both [CoH( tBudPNP)] and [CoEt( tBudPNP)], which are more challenging (hydride) or not possible (ethyl) to prepare with the parent PNP ligand. Electrochemical measurements with both the Co and Ni dPNP species demonstrate a substantial shift in redox potentials for both the M(II/III) and M(II/I) couples. In the case of the former, oxidation to trivalent Co was found to be reversible, and subsequent reaction with AgSbF6 afforded a rare example of a square-planar Co(III) species. Corresponding reduction of [CoCl( tBudPNP)] with KC8 produced the diamagnetic Co(I) species, [Co(N2)( tBudPNP)]. Further reduction of the Co(I) complex was found to generate a pincer-based π-radical anion that demonstrated well-resolved EPR features to the four hydrogen atoms and lone nitrogen atom of the ligand with minor contributions from cobalt and coordinated N2. Changes in the electronic character of the PNP ligand upon dehydrogenation are proposed to result from loss of aromaticity in the pyrrole ligand, resulting in a more reducing central amido donor. DFT calculations on the Co(II) complexes were performed to shed further insight into the electronic structure of the pincer complexes.

Near-infrared C-term MCD spectroscopy of octahedral uranium(V) complexes.

C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d-d and f-f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(v) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f-f transitions of [UCl6]- and [UF6]- are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7 → Γ8 transitions in [UF6]-. The experimental NIR MCD studies were further extended to [U(OC6F5)6]-, [U(CH2SiMe3)6]-, and [U(NC(tBu)(Ph))6]- to evaluate the effects of ligand-type on the f-f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f-f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(v) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(v) complexes and identify areas for continued theoretical development.