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1. Concerted proton–electron transfer reactions of manganese–hydroxo and manganese–oxo complexes

   https://doi.org/10.1039/d0cc01201g  

   Mayfield, Jaycee R. ; Grotemeyer, Elizabeth N. ; Jackson, Timothy A. ( January 2020 , Chemical Communications)

   The enzymes manganese superoxide dismutase and manganese lipoxygenase use Mn III –hydroxo centres to mediate proton-coupled electron transfer (PCET) reactions with substrate. As manganese is earth-abundant and inexpensive, manganese catalysts are of interest for synthetic applications. Recent years have seen exciting reports of enantioselective C–H bond oxidation by Mn catalysts supported by aminopyridyl ligands. Such catalysts offer economic and environmentally-friendly alternatives to conventional reagents and catalysts. Mechanistic studies of synthetic catalysts highlight the role of Mn–oxo motifs in attacking substrate C–H bonds, presumably by a concerted proton–electron transfer (CPET) step. (CPET is a sub-class of PCET, where the proton and electron are transferred in the same step.) Knowledge of geometric and electronic influences for CPET reactions of Mn–hydroxo and Mn–oxo adducts enhances our understanding of biological and synthetic manganese centers and informs the design of new catalysts. In this Feature article, we describe kinetic, spectroscopic, and computational studies of Mn III –hydroxo and Mn IV –oxo complexes that provide insight into the basis for the CPET reactivity of these species. Systematic perturbations of the ligand environment around Mn III –hydroxo and Mn IV –oxo motifs permit elucidation of structure–activity relationships. For Mn III –hydroxo centers, electron-deficient ligands enhance oxidative reactivity.more »However, ligand perturbations have competing consequences, as changes in the Mn III/II potential, which represents the electron-transfer component for CPET, is offset by compensating changes in the p K a of the Mn II –aqua product, which represents the proton-transfer component for CPET. For Mn IV –oxo systems, a multi-state reactivity model inspired the development of significantly more reactive complexes. Weakened equatorial donation to the Mn IV –oxo unit results in large rate enhancements for C–H bond oxidation and oxygen-atom transfer reactions. These results demonstrate that the local coordination environment can be rationally changed to enhance reactivity of Mn III –hydroxo and Mn IV –oxo adducts.« less
2. Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster

   https://doi.org/10.1039/D2SC04843D  

   Cooney, Shannon E. ; Fertig, Alex A. ; Buisch, Madeleine R. ; Brennessel, William W. ; Matson, Ellen M. ( November 2022 , Chemical Science)

   Hydrogen-atom (H-atom) transfer at the surface of heterogeneous metal oxides has received significant attention owing to its relevance in energy conversion and storage processes. Here, we present the synthesis and characterization of an organofunctionalized polyoxovanadate cluster, (calix)V6O5(OH2)(OMe) 8 (calix = 4- tert -butylcalix[4]arene). Through a series of equilibrium studies, we establish the BDFE(O–H) avg of the aquo ligand as 62.4 ± 0.2 kcal mol −1 , indicating substantial bond weaking of water upon coordination to the cluster surface. Subsequent kinetic isotope effect studies and Eyring analysis indicate the mechanism by which the hydrogenation of organic substrates occurs proceeds through a concerted proton–electron transfer from the aquo ligand. Atomistic resolution of surface reactivity presents a novel route of hydrogenation reactivity from metal oxide surfaces through H-atom transfer from surface-bound water molecules.
3. Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

   https://doi.org/10.1039/D2SC04210J  

   Szczepaniak, Grzegorz ; Jeong, Jaepil ; Kapil, Kriti ; Dadashi-Silab, Sajjad ; Yerneni, Saigopalakrishna S. ; Ratajczyk, Paulina ; Lathwal, Sushil ; Schild, Dirk J. ; Das, Subha R. ; Matyjaszewski, Krzysztof ( October 2022 , Chemical Science)

   Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access to well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in the synthesis of polymer biohybrids. Herein, inspired by the photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, we demonstrate a dual photoredox/copper catalysis that allows open-air ATRP under green light irradiation. Eosin Y was used as an organic photoredox catalyst (PC) in combination with a copper complex (X–Cu II /L). The role of PC was to trigger and drive the polymerization, while X–Cu II /L acted as a deactivator, providing a well-controlled polymerization. The excited PC was oxidatively quenched by X–Cu II /L, generating Cu I /L activator and PC˙ + . The ATRP ligand (L) used in excess then reduced the PC˙ + , closing the photocatalytic cycle. The continuous reduction of X–Cu II /L back to Cu I /L by excited PC provided high oxygen tolerance. As a result, a well-controlled and rapid ATRP could proceed even in an open vessel despite continuous oxygen diffusion. This method allowed the synthesis ofmore »polymers with narrow molecular weight distributions and controlled molecular weights using Cu catalyst and PC at ppm levels in both aqueous and organic media. A detailed comparison of photo-ATRP with PET-RAFT polymerization revealed the superiority of dual photoredox/copper catalysis under biologically relevant conditions. The kinetic studies and fluorescence measurements indicated that in the absence of the X–Cu II /L complex, green light irradiation caused faster photobleaching of eosin Y, leading to inhibition of PET-RAFT polymerization. Importantly, PET-RAFT polymerizations showed significantly higher dispersity values (1.14 ≤ Đ ≤ 4.01) in contrast to photo-ATRP (1.15 ≤ Đ ≤ 1.22) under identical conditions.« less
4. Trimerization and cyclization of reactive P-functionalities confined within OCO pincers

   https://doi.org/10.1039/d1ra05926b  

   Chinen, Beatrice L. ; Hyvl, Jakub ; Brayton, Daniel F. ; Riek, Matthew M. ; Yoshida, Wesley Y. ; Chapp, Timothy W. ; Rheingold, Arnold L. ; Cain, Matthew F. ( August 2021 , RSC Advances)

   In order to stabilize a 10–P–3 species with C 2v symmetry and two lone pairs on the central phosphorus atom, a specialized ligand is required. Using an NCN pincer, previous efforts to enforce this planarized geometry at P resulted in the formation of a C s -symmetric, 10π-electron benzazaphosphole that existed as a dynamic “bell-clapper” in solution. Here, OCO pincers 1 and 2 were synthesized, operating under the hypothesis that the more electron-withdrawing oxygen donors would better stabilize the 3-center, 4-electron O–P–O bond of the 10–P–3 target and the sp 3 -hybridized benzylic carbon atoms would prevent the formation of aromatic P-heterocycles. However, subjecting 1 to a metalation/phosphination/reduction sequence afforded cyclotriphosphane 3, resulting from trimerization of the P( i ) center unbound by its oxygen donors. Pincer 2 featuring four benzylic CF 3 groups was expected to strengthen the O–P–O bond of the target, but after metal–halogen exchange and quenching with PCl 3 , unexpected cyclization with loss of CH 3 Cl was observed to give monochlorinated 5. Treatment of 5 with ( p -CH 3 )C 6 H 4 MgBr generated crystalline P-( p -Tol) derivative 6, which was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. Themore »complex 19 F NMR spectra of 5 and 6 observed experimentally, were reproduced by simulations with MestreNova.« less
5. Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

   https://doi.org/10.1002/ange.202212488  

   Senthil, Shuruthi ; Kwon, Seongyeon ; Fehn, Dominik ; Im, Hoyoung ; Gau, Michael R. ; Carroll, Patrick J. ; Baik, Mu‐Hyun ; Meyer, Karsten ; Mindiola, Daniel J. ( November 2022 , Angewandte Chemie)

   Decarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO⁻, to the Nb^IVcomplex [(PNP)NbCl₂(N^tBuAr)] (1) (PNP=N[2‐PⁱPr₂‐4‐methylphenyl]₂⁻; Ar=3,5‐Me₂C₆H₃) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(N^tBuAr)] (2). Reduction of2with CoCp*₂cleaves the P−P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(N^tBuAr)] (3). Theoretical studies have been used to understand both the coupling of the P‐atom and the reductive cleavage of the P−P bond. Reaction of3with a two‐electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P−P coupled ligand, namely [(PNPP)Nb=S(N^tBuAr)] (4).