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• Martínez-Laguna, Jonathan; Schmidtke, Inga Lena; Monti, Andrea; Rama, Raquel J.; Sánchez-Rodas, Daniel & Nicasio, M. Carmen [Vis alle 9 forfattere av denne artikkelen] (2026). Iridium-mediated methane dehydrogenation and methylidene (=CH<inf>2</inf>) transfer. Chem. ISSN 2451-9308. doi: 10.1016/j.chempr.2026.102999. Fulltekst i vitenarkiv
• Gerz, Isabelle; Aunan, Erlend; Finelli, Valeria; Rasheed, Mouhammad Abu; Deplano, Gabriele & Pupo, Rafael Cortez Sgroi [Vis alle 15 forfattere av denne artikkelen] (2024). Enabling a bioinspired N,N,N-copper coordination motif through spatial control in UiO-67: synthesis and reactivity. Dalton Transactions. ISSN 1477-9226. 53, s. 8141–8153. doi: 10.1039/d3dt03096b. Fulltekst i vitenarkiv Vis sammendrag

  Metal–organic frameworks (MOFs) featuring zirconium-based clusters are widely used for the development of functionalized materials due to their exceptional stability. In this study, we report the synthesis of a novel N,N,N-ligand compatible with a biphenyl dicarboxylic acid-based MOF. However, the resulting copper(I) complex exhibited unexpected coordination behaviour, lacking the intended trifold coordination motif. Herein, we demonstrate the successful immobilization of a bioinspired ligand within the MOF, which preserved its crystalline and porous nature while generating a well-defined copper site. Comprehensive spectroscopic analyses, including X-ray absorption, UV/Vis, and infrared spectroscopy, were conducted to investigate the copper site and its thermal behaviour. The immobilized ligand exhibited the desired tridentate coordination to copper, providing access to a coordination motif otherwise unattainable. Notably, water molecules were also found to coordinate to copper. Upon heating, the copper centre within the MOF exhibited reversible dehydration, suggesting facile creation of open coordination sites. Furthermore, the copper site displayed reduction at elevated temperatures and subsequent susceptibility to oxidation by molecular oxygen. Lastly, both the molecular complexes and the MOF were evaluated as catalysts for the oxidation of cyclohexane using hydrogen peroxide. This work highlights the successful immobilization of a bioinspired ligand in a zirconium-based MOF, shedding light on the structural features, thermal behaviour, and catalytic potential of the resulting copper sites.

• Pintea, Maria; Mason, Nigel; Peiró-Franch, Anna; Clark, Ewan; Samanta, Kushal & Glessi, Cristiano [Vis alle 8 forfattere av denne artikkelen] (2023). Dissociative electron attachment to gold(I)-based compounds: 4,5-dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I). Frontiers in Chemistry. 11. doi: 10.3389/fchem.2023.1028008. Fulltekst i vitenarkiv Vis sammendrag

  With the use of proton-NMR and powder XRD (XRPD) studies, the suitability of specific Au-focused electron beam induced deposition (FEBID) precursors has been investigated with low electron energy, structure, excited states and resonances, structural crystal modifications, flexibility, and vaporization level. 4,5-Dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I) is a compound that is a uniquely designed precursor to meet the needs of focused electron beam-induced deposition at the nanostructure level, which proves its capability in creating high purity structures, and its growing importance in other AuIm x and AuCl n B (where x and n are the number of radicals, B = CH, CH 3 , or Br) compounds in the radiation cancer therapy increases the efforts to design more suitable bonds in processes of SEM (scanning electron microscopy) deposition and in gas-phase studies. The investigation performed of its powder shape using the XRPD XPERT 3 panalytical diffractometer based on CoK α lines shows changes to its structure with change in temperature, level of vacuum, and light; the sensitivity of this compound makes it highly interesting in particular to the radiation research. Used in FEBID, though its smaller number of C, H, and O atoms has lower levels of C contamination in the structures and on the surface, it replaces these bonds with C–Cl and C–N bonds that have lower bond-breaking energy. However, it still needs an extra purification step in the deposition process, either H 2 O, O 2 , or H jets.

• Hylland, Knut Tormodssønn; Schmidtke, Inga; Wragg, David Stephen; Nova, Ainara & Tilset, Mats (2022). Synthesis of substituted (N,C) and (N,C,C) Au(iii) complexes: the influence of sterics and electronics on cyclometalation reactions. Dalton Transactions. ISSN 1477-9226. 51(13), s. 5082–5097. doi: 10.1039/d2dt00371f. Fulltekst i vitenarkiv Vis sammendrag

  Cyclometalated Au(III) complexes are of interest due to their catalytic, medicinal, and photophysical properties. Herein, we describe the synthesis of derivatives of the type (N,C)Au(OAcF)2 (OAcF = trifluoroacetate) and (N,C,C)AuOAcF by a cyclometalation route, where (N,C) and (N,C,C) are chelating 2-arylpyridine ligands. The scope of the synthesis is explored by substituting the 2-arylpyridine core with electron donor or acceptor substituents at one or both rings. Notably, a variety of functionalized Au(III) complexes can be obtained in one step from the corresponding ligand and Au(OAc)3, eliminating the need for organomercury intermediates, which is commonly reported for similar syntheses. The influence of substituents in the ligand backbone on the resulting complexes was assessed using DFT calculations, 15N NMR spectroscopy and single-crystal X-ray diffraction analysis. A correlation between the electronic properties of the (N,C) ligands and their ability to undergo cyclometalation was found from experimental studies combined with natural charge analysis, suggesting the cyclometalation at Au(III) to take place via an electrophilic aromatic substitution-type mechanism. The formation of Au(III) pincer complexes from tridentate (N,C,C) ligands was investigated by synthesis and DFT calculations, in order to assess the feasibility of C(sp3)–H bond activation as a synthetic pathway to (N,C,C) cyclometalated Au(III) complexes. It was found that C(sp3)–H bond activation is feasible for ligands containing different alkyl groups (isopropyl and ethyl), although the C–H activation is less energetically favored compared to a ligand containing tert-butyl groups.

• Pizarro, Juan Diego; Schmidtke, Inga; Nova, Ainara; Fructos, Manuel R. & Pérez, Pedro J. (2022). Selective Functionalization of Arene C(sp2)-H Bonds by Gold Catalysis: The Role of Carbene Substituents. ACS Catalysis. 12(12), s. 6851–6856. doi: 10.1021/acscatal.2c01713. Fulltekst i vitenarkiv Vis sammendrag

  The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)CO2Et fragment, which dramatically affects the energy profile of this transformation.

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• Schmidtke, Inga Lena; Erken, Christina; Aguilera, Abril Castro; Repo, Timo & Flores, Ainara Nova (2025). Ethylene hydrogenation mediated by Rhodium(I)-hydride: mechanistic insights. Fulltekst i vitenarkiv
• Schmidtke, Inga Lena; Erken, Christina; Aguilera, Abril Castro; Repo, Timo & Flores, Ainara Nova (2025). Mechanistic insights into Ethylene hydrogenation mediated by Rhodium(I)-monohydride. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Repo, Timo & Flores, Ainara Nova (2024). Mechanistic DFT studies on the formation of a novel Rh(I)-ethylene complex. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Repo, Timo & Flores, Ainara Nova (2024). Computational insights into ethylene hydrogenation via Rh(III)-dimers. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Castro, Abril C; Repo, Timo & Flores, Ainara Nova (2024). Ethylene hydrogenation via Rh(III)-dimers: a mechanistic study. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Repo, Timo & Flores, Ainara Nova (2024). Ethylene hydrogenation via Rh(III)-dimers: a mechanistic study. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Repo, Timo & Flores, Ainara Nova (2023). Mechanistic DFT studies of the formation of a novel Rh(I)-ethylene complex. Fulltekst i vitenarkiv
• Schmidtke, Inga; Erken, Christina; Repo, Timo & Flores, Ainara Nova (2023). Mechanistic DFT studies on the formation of a novel Rh(I)-ethylene complex. Fulltekst i vitenarkiv
• Schmidtke, Inga; Pizarro, Juan Diego; Fructos, Manuel R.; Pérez, Pedro J. & Nova, Ainara (2022). Selective functionalization of arene C(sp2)-H bonds by gold catalysis. Fulltekst i vitenarkiv
• Schmidtke, Inga; Pizarro, Juan Diego; Fructos, Manuel R.; Pérez, Pedro J. & Nova, Ainara (2022). Selective functionalization of arene C(sp2)-H bonds by gold catalysis. Fulltekst i vitenarkiv
• Schmidtke, Inga; Pizarro, Juan Diego; Fructos, Manuel R.; Pérez, Pedro J. & Nova, Ainara (2022). Computational study on the role of carbene substituents in a Au(I)-catalyzed C-H-functionalization reaction. Fulltekst i vitenarkiv

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