TY  - JOUR
A1  - Zhang, Xiaolei
A1  - Friedrich, Alexandra
A1  - Marder, Todd B.
T1  - Copper-Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
JF  - Chemistry—A European Journal
N2  - Herein, the copper-catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B\(_{2}\)pin\(_{2}\)) or bis(neopentane glycolato)diboron (B\(_{2}\)neop\(_{2}\)) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon-skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N-methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late-stage conversion of carboxylic acid-containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p-toluoyl chloride and an NHC-copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.
KW  - boronate
KW  - catalysis
KW  - borylation
KW  - carbonyl
KW  - copper
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318318
VL  - 28
IS  - 42
ER  - 
TY  - JOUR
A1  - Föhrenbacher, Steffen A.
A1  - Krahfuss, Mirjam J.
A1  - Zapf, Ludwig
A1  - Friedrich, Alexandra
A1  - Ignat'ev, Nikolai V.
A1  - Finze, Maik
A1  - Radius, Udo
T1  - Tris(pentafluoroethyl)difluorophosphorane: a versatile fluoride acceptor for transition metal chemistry
JF  - Chemistry Europe
N2  - Fluoride abstraction from different types of transition metal fluoride complexes [L\(_n\)MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C\(_2\)F\(_5\))\(_3\)PF\(_2\) to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C\(_2\)F\(_5\))\(_3\)PF\(_3\)]\(^-\)) is reported. (C\(_2\)F\(_5\))\(_3\)PF\(_2\) reacted with trans-[Ni(iPr\(_2\)Im)\(_2\)(Ar\(^F\))F] (iPr2Im=1,3-diisopropylimidazolin-2-ylidene; Ar\(^F\)=C\(_6\)F\(_5\), 1 a; 4-CF\(_3\)-C\(_6\)F\(_4\), 1 b; 4-C\(_6\)F\(_5\)-C\(_6\)F\(_4\), 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr\(_2\)Im)\(_2\)(solv)(Ar\(^F\))]FAP (2 a-c[solv]; solv=Et\(_2\)O, CH\(_2\)Cl\(_2\), THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh\(_3\), solvent coordination was suppressed and the complexes trans-[Ni(iPr\(_2\)Im)\(_2\)(PPh\(_3\))(C\(_6\)F\(_5\))]FAP (trans-2 a[PPh\(_3\)]) and cis-[Ni(iPr\(_2\)Im)\(_2\)(Dipp\(_2\)Im)(C\(_6\)F\(_5\))]FAP (cis-2 a[Dipp\(_2\)Im]) (Dipp\(_2\)Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp\(_2\)Im)CuF] (3) in CH\(_2\)Cl\(_2\) or 1,2-difluorobenzene led to the isolation of [{(Dipp\(_2\)Im)Cu}\(_2\)]\(^2\)\(^+\)2 FAP\(^-\) (4). Subsequent reaction of 4 with PPh\(_3\) and different carbenes resulted in the complexes [(Dipp\(_2\)Im)Cu(LB)]FAP (5 a–e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp\(_2\)Im)Cu(C\(_6\)Me\(_6\))]FAP (5 f), which serves as a source of [(Dipp\(_2\)Im)Cu)]\(^+\). Fluoride abstraction of [Cp\(_2\)TiF\(_2\)] (7) resulted in the formation of dinuclear [FCp\(_2\)Ti(μ-F)TiCp\(_2\)F]FAP (8) (Cp=η\(^5\)-C\(_5\)H\(_5\)) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.
KW  - inorganic chemistry
KW  - copper
KW  - nickel
KW  - phosphoranes
KW  - titanium
KW  - weakly coordinating anions
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256665
VL  - 27
IS  - 10
ER  - 
TY  - JOUR
A1  - Schneider, Leon N.
A1  - Tanzer Krauel, Eva-Maria
A1  - Deutsch, Carl
A1  - Urbahns, Klaus
A1  - Bischof, Tobias
A1  - Maibom, Kristina A. M.
A1  - Landmann, Johannes
A1  - Keppner, Fabian
A1  - Kerpen, Christoph
A1  - Hailmann, Michael
A1  - Zapf, Ludwig
A1  - Knuplez, Tanja
A1  - Bertermann, Rüdiger
A1  - Ignat'ev, Nikolai V.
A1  - Finze, Maik
T1  - Stable and Storable N(CF\(_{3}\))\(_{2}\) Transfer Reagents
JF  - Chemistry—A European Journal
N2  - Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF\(_{3}\))\(_{2}\) group are rare. One reason is that transfer reagents are scarce and metal-based storable reagents are unknown. Herein, a set of Cu\(^{I}\) and Ag\(^{I}\) bis(trifluoromethyl)amido complexes stabilized by N- and P-donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl)amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis(trifluoromethyl)amines, 2-bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N-bis(trifluoromethyl)glycine.
KW  - silver
KW  - amination
KW  - copper
KW  - fluorinated ligands
KW  - N ligands
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256890
VL  - 27
IS  - 42
ER  - 
TY  - JOUR
A1  - Lorkowski, Jan
A1  - Krahfuß, Mirjam
A1  - Kubicki, Maciej
A1  - Radius, Udo
A1  - Pietraszuk, Cezary
T1  - Intramolecular Ring‐Expansion Reaction (RER) and Intermolecular Coordination of In Situ Generated Cyclic (Amino)(aryl)carbenes (cAArCs)
JF  - Chemistry – A European Journal
N2  - Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α‐elimination of 3‐alkoxyisoindolines at high temperatures or by deprotonation of isoindol‐2‐ium chlorides with sodium or copper(I) acetates at low temperatures. 3‐Alkoxy‐isoindolines 2 a,b‐OR (R=Me, Et, iPr) have been prepared in high yields by the addition of a solution of 2‐aryl‐1,1‐diphenylisoindol‐2‐ium triflate (1 a,b‐OTf; a: aryl=Dipp=2,6‐diisopropylphenyl; b: Mesityl‐, Mes=2,4,6‐trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a,b‐OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol‐2‐ium chlorides 1 a,b‐Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a. Without any additional trapping reagent, in situ generation of 1,1‐diphenylisoidolin‐3‐ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C−H bond of a phenyl substituent, followed by ring‐expansion reaction; namely, anthracene derivatives 9‐N(H)aryl‐10‐Ph‐C14H8 4 a,b (a: Dipp; b: Mes). These compounds are conveniently synthesized by deprotonation of the isoindol‐2‐ium chlorides with sodium acetate in high yields. Deprotonation of 1 a‐Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a, and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].
KW  - cAArC
KW  - complexes
KW  - copper
KW  - NHC
KW  - ring-expansion reaction
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-212496
VL  - 25
IS  - 48
SP  - 11365
EP  - 11374
ER  - 
TY  - JOUR
A1  - Lorkowski, Jan
A1  - Krahfuss, Mirjam
A1  - Kubicki, Maciej
A1  - Radius, Udo
A1  - Pietraszuk, Cezary
T1  - Intramolecular ring expansion reaction (RER) and intermolecular coordination of in situ generated Cyclic (Amino)(Aryl)Carbenes (cAArCs)
JF  - Chemistry - A European Journal
N2  - Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α‐elimination of 3‐alkoxyisoindolines at high temperatures or by deprotonation of isoindol‐2‐ium chlorides with sodium or copper(I) acetates at low temperatures. 3‐Alkoxy‐isoindolines 2 a ,b‐OR (R=Me, Et, i Pr) have been prepared in high yields by the addition of a solution of 2‐aryl‐1,1‐diphenylisoindol‐2‐ium triflate (1 a ,b‐OTf ; a : aryl=Dipp=2,6‐diisopropylphenyl; b : Mesityl‐, Mes=2,4,6‐trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a ,b‐OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol‐2‐ium chlorides 1 a ,b‐Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a . Without any additional trapping reagent, in situ generation of 1,1‐diphenylisoidolin‐3‐ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C−H bond of a phenyl substituent, followed by ring‐expansion reaction; namely, anthracene derivatives 9‐N(H)aryl‐10‐Ph‐C14H8 4 a ,b (a : Dipp; b : Mes). These compounds are conveniently synthesized by deprotonation of the isoindol‐2‐ium chlorides with sodium acetate in high yields. Deprotonation of 1 a‐Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a , and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].
KW  - cAArC
KW  - complexes
KW  - copper
KW  - NHC
KW  - ring-expansion reaction
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-204847
VL  - 25
IS  - 48
ER  - 
TY  - JOUR
A1  - Lousada, Cláudio M.
A1  - Soroka, Inna L.
A1  - Yagodzinskyy, Yuriy
A1  - Tarakina, Nadezda V.
A1  - Todoshchenko, Olga
A1  - Hänninen, Hannu
A1  - Korzhavyi, Pavel A.
A1  - Jonsson, Mats
T1  - Gamma radiation induces hydrogen absorption by copper in water
JF  - Scientific Reports
N2  - One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H\(_{2}\)(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.
KW  - gamma radiation
KW  - radioactive waste
KW  - nuclear power
KW  - repositories
KW  - safety
KW  - copper
KW  - water
Y1  - 2016
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-167730
VL  - 6
IS  - 24234
ER  -