Category: Research

Title:
Pd-Catalyzed Difluoromethylations of Aryl Boronic Acids, Halides, and Pseudohalides with ICF₂H Generated ex Situ

Abstract:
An expedient ex-situ generation of difluoroiodomethane (DFIM) and its immediate use in a Pd-catalyzed difluoromethylation of aryl boronic acids and ester derivatives in a two-chamber reactor is reported. Heating a solution of bromodifluoroacetic acid with sodium iodide in sulfolane proved to be effective for the generation of near stoichiometric amounts of DFIM for the ensuing catalytic coupling step. A two-step difluoromethylation of aryl (pseudo)halides with tetrahydroxydiboron as a low-cost reducing agent, both promoted by Pd catalysis, proved effective to install this fluorine-containing C₁ group onto several pharmaceutically relevant molecules. Finally, the method proved adaptable to deuterium incorporation by simply adding D₂O to the DFIM-generating chamber.

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Title:
Microscopic Insights into Cation-Coupled Electron Hopping Transport in a Metal–Organic Framework

Abstract:
Electron transport through metal–organic frameworks by a hopping mechanism between discrete redox active sites is coupled to diffusion-migration of charge-balancing counter cations. Experimentally determined apparent diffusion coefficients, D_e^app, that characterize this form of charge transport thus contain contributions from both processes. While this is well established for MOFs, microscopic descriptions of this process are largely lacking. Herein, we systematically lay out different scenarios for cation-coupled electron transfer processes that are at the heart of charge diffusion through MOFs. Through systematic variations of solvents and electrolyte cations, it is shown that the D_e^app for charge migration through a PIZOF-type MOF, Zr(dcphOH-NDI) that is composed of redox-active naphthalenediimide (NDI) linkers, spans over 2 orders of magnitude. More importantly, however, the microscopic mechanisms for cation-coupled electron propagation are contingent on differing factors depending on the size of the cation and its propensity to engage in ion pairs with reduced linkers, either non-specifically or in defined structural arrangements. Based on computations and in agreement with experimental results, we show that ion pairing generally has an adverse effect on cation transport, thereby slowing down charge transport. In Zr(dcphOH-NDI), however, specific cation–linker interactions can open pathways for concerted cation-coupled electron transfer processes that can outcompete limitations from reduced cation flux.

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The first NordCO₂ collaboration paper of the year is from UiT and HU, involving PhD students Aleksi (HU), Dat (UiT), and Jere (HU) from Kathrin’s and Timo’s groups. Together, they studied the the synthesis of butyrolactones from CO₂ using  titanacyclopropane as mediator.

Title:
Titanium isopropoxide-mediated cis-selective synthesis of 3,4-substituted butyrolactones from CO₂

Abstract:
We report a Ti(OiPr)₄-mediated multicomponent reaction, which produces 3,4-substituted cis-δ-lactones from alkyl magnesium chloride, benzaldehyde and CO₂. The key intermediate, titanacyclopropane, is formed in situ from Ti(OiPr)₄ and a Grignard reagent, which enables 1,2-dinucleophilic reactivity that is used to insert carbon dioxide and an aldehyde. An alternative reaction route is also described where a primary alkene is used to create the titanacyclopropane. A computational analysis of the elementary steps shows that the carbon dioxide and the aldehyde insertion proceeds through an inner-sphere mechanism. A variety of cis-butyrolactones can be synthesized with up to 7 : 1 diastereoselectivity and 77% yield.

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NordCO₂ postdoc Ljiljana Pavlovic and PI Kathrin Hopmann have collaborated with the Hazari Group from Yale for their study on “the insertion of CO₂ into palladium and nickel methyl complexes supported by ^RPBP […] pincer ligands”. They performed the computational analysis part of the study, where they investigated the plausible pathways for insertion.

Title:
Ligand and solvent effects on CO₂ insertion into group 10 metal alkyl bonds

Abstract:
The insertion of carbon dioxide into metal element σ-bonds is an important elementary step in many catalytic reactions for carbon dioxide valorization. Here, the insertion of carbon dioxide into a family of group 10 alkyl complexes of the type (^RPBP)M(CH₃) (^RPBP = B(NCH₂PR₂)₂C₆H₄⁻; R = Cy or ^tBu; M = Ni or Pd) to generate κ¹-acetate complexes of the form (^RPBP)M{OC(O)CH₃} is investigated. This involved the preparation and characterization of a number of new complexes supported by the unusual ^RPBP ligand, which features a central boryl donor that exerts a strong trans-influence, and the identification of a new decomposition pathway that results in C–B bond formation. In contrast to other group 10 methyl complexes supported by pincer ligands, carbon dioxide insertion into (^RPBP)M(CH₃) is facile and occurs at room temperature because of the high trans-influence of the boryl donor. Given the mild conditions for carbon dioxide insertion, we perform a rare kinetic study on carbon dioxide insertion into a late-transition metal alkyl species using (^tBuPBP)Pd(CH₃). These studies demonstrate that the Dimroth–Reichardt parameter for a solvent correlates with the rate of carbon dioxide insertion and that Lewis acids do not promote insertion. DFT calculations indicate that insertion into (^tBuPBP)M(CH₃) (M = Ni or Pd) proceeds via an S_E2 mechanism and we compare the reaction pathway for carbon dioxide insertion into group 10 methyl complexes with insertion into group 10 hydrides. Overall, this work provides fundamental insight that will be valuable for the development of improved and new catalysts for carbon dioxide utilization.

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The research groups led by NordCO₂ PIs Kim Daasbjerg and Troels Skrydstrup from Aarhus as well as Mårten Ahlquist from KTH Royal Institute of Technology have released a new paper where they explore the effect of additives for the electroreduction of CO₂ to HCOOH, using a manganese electrocatalyst. Congratulations to all authors!

Title:
Promoting Selective Generation of Formic Acid from CO₂ Using Mn(bpy)(CO)₃Br as Electrocatalyst and Triethylamine/Isopropanol as Additives

Abstract:
Urgent solutions are needed to efficiently convert the greenhouse gas CO₂ into higher-value products. In this work, fac-Mn(bpy)(CO)₃Br (bpy = 2,2′-bipyridine) is employed as electrocatalyst in reductive CO₂ conversion. It is shown that product selectivity can be shifted from CO toward HCOOH using appropriate additives, i.e., Et₃N along with iPrOH. A crucial aspect of the strategy is to outrun the dimer-generating parent-child reaction involving fac-Mn(bpy)(CO)₃Br and [Mn(bpy)(CO)₃]⁻ and instead produce the Mn hydride intermediate. Preferentially, this is done at the first reduction wave to enable formation of HCOOH at an overpotential as low as 260 mV and with faradaic efficiency of 59 ± 1%. The latter may be increased to 71 ± 3% at an overpotential of 560 mV, using 2 M concentrations of both Et₃N and iPrOH. The nature of the amine additive is crucial for product selectivity, as the faradaic efficiency for HCOOH formation decreases to 13 ± 4% if Et₃N is replaced with Et₂NH. The origin of this difference lies in the ability of Et₃N/iPrOH to establish an equilibrium solution of isopropyl carbonate and CO₂, while with Et₂NH/iPrOH, formation of the diethylcarbamic acid is favored. According to density-functional theory calculations, CO₂ in the former case can take part favorably in the catalytic cycle, while this is less opportune in the latter case because of the CO₂-to-carbamic acid conversion. This work presents a straightforward procedure for electrochemical reduction of CO₂ to HCOOH by combining an easily synthesized manganese catalyst with commercially available additives.

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