PhenTAA: A Redox-Active N4-Macrocyclic Ligand Featuring Donor and Acceptor Moieties.

Here, we present the development and characterization of the novel PhenTAA macrocycle as well as a series of [Ni(R2PhenTAA)]n complexes featuring two sites for ligand-centered redox-activity. These differ in the substituent R (R = H, Me, or Ph) and overall charge of the complex n (n = -2, -1, 0, +1, or +2). Electrochemical and spectroscopic techniques (CV, UV/vis-SEC, X-band EPR) reveal that all redox events of the [Ni(R2PhenTAA)] complexes are ligand-based, with accessible ligand charges of -2, -1, 0, +1, and +2. The o-phenylenediamide (OPD) group functions as the electron donor, while the imine moieties act as electron acceptors. The flanking o-aminobenzaldimine groups delocalize spin density in both the oxidized and reduced ligand states. The reduced complexes have different stabilities depending on the substituent R. For R = H, dimerization occurs upon reduction, whereas for R = Me/Ph, the reduced imine groups are stabilized. This also gives electrochemical access to a [Ni(R2PhenTAA)]2- species. DFT and TD-DFT calculations corroborate these findings and further illustrate the unique donor-acceptor properties of the respective OPD and imine moieties. The novel [Ni(R2PhenTAA)] complexes exhibit up to five different ligand-based oxidation states and are electrochemically stable in a range from -2.4 to +1.8 V for the Me/Ph complexes (vs Fc/Fc+).

Understanding Off-Cycle and Deactivation Pathways in Radical-Type Carbene Transfer Catalysis.

Transition metal radical-type carbene transfer catalysis is a sustainable and atom-efficient method to generate C-C bonds, especially to produce fine chemicals and pharmaceuticals. A significant amount of research has therefore been devoted to applying this methodology, which resulted in innovative routes toward otherwise synthetically challenging products and a detailed mechanistic understanding of the catalytic systems. Furthermore, combined experimental and theoretical efforts elucidated the reactivity of carbene radical complexes and their off-cycle pathways. The latter can imply the formation of N-enolate and bridging carbenes, and undesired hydrogen atom transfer by the carbene radical species from the reaction medium which can lead to catalyst deactivation. In this concept paper, we demonstrate that understanding off-cycle and deactivation pathways not only affords solutions to circumvent them, but can also uncover novel reactivity for new applications. In particular, considering off-cycle species involved in metalloradical catalysis can stimulate further development of radical-type carbene transfer reactions.

Carbene Radicals in Transition-Metal-Catalyzed Reactions.

Discovered as organometallic curiosities in the 1970s, carbene radicals have become a staple in modern-day homogeneous catalysis. Carbene radicals exhibit nucleophilic radical-type reactivity orthogonal to classical electrophilic diamagnetic Fischer carbenes. Their successful catalytic application has led to the synthesis of a myriad of carbo- and heterocycles, ranging from simple cyclopropanes to more challenging eight-membered rings. The field has matured to employ densely functionalized chiral porphyrin-based platforms that exhibit high enantio-, regio-, and stereoselectivity. Thus far the focus has largely been on cobalt-based systems, but interest has been growing for the past few years to expand the application of carbene radicals to other transition metals. This Perspective covers the advances made since 2011 and gives an overview on the coordination chemistry, reactivity, and catalytic application of carbene radical species using transition metal complexes and catalysts.

Cobalt(II)-tetraphenylporphyrin-catalysed carbene transfer from acceptor-acceptor iodonium ylides via N-enolate-carbene radicals.

Square-planar cobalt(II) systems have emerged as powerful carbene transfer catalysts for the synthesis of numerous (hetero)cyclic compounds via cobalt(III)-carbene radical intermediates. Spectroscopic detection and characterization of reactive carbene radical intermediates is limited to a few scattered experiments, centered around monosubstituted carbenes. Here, we reveal the formation of disubstituted cobalt(III)-carbene radicals derived from a cobalt(II)-tetraphenylporphyrin complex and acceptor-acceptor λ3-iodaneylidenes (iodonium ylides) as carbene precursors and their catalytic application. Iodonium ylides generate biscarbenoid species via reversible ligand modification of the paramagnetic cobalt(II)-tetraphenylporphyrin complex catalyst. Two interconnected catalytic cycles are involved in the overall mechanism, with a monocarbene radical and an N-enolate-carbene radical intermediate at the heart of each respective cycle. Notably, N-enolate formation is not a deactivation pathway but a reversible process, enabling transfer of two carbene moieties from a single N-enolate-carbene radical intermediate. The findings are supported by extensive experimental and computational studies.