Refine
Has Fulltext
- yes (73)
Is part of the Bibliography
- yes (73)
Year of publication
- 2021 (73) (remove)
Document Type
- Journal article (54)
- Doctoral Thesis (19)
Keywords
- boron (13)
- inorganic chemistry (11)
- luminescence (5)
- Bor (4)
- boranes (4)
- borylation (4)
- density functional calculations (4)
- Boron (3)
- Heterocyclische Carbene <-N> (3)
- Konjugierte Polymere (3)
Institute
- Institut für Anorganische Chemie (73) (remove)
Sonstige beteiligte Institutionen
In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{−1}\) and 3.42×107 M\(^{−1}\) in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn\(^{-7}\)HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.
π-Conjugated oligomers and polymers with tricoordinate boron centers incorporated into the main chain have attracted considerable attention as the interaction of the vacant p orbital on boron with an adjacent π system of the chain leads to conjugated materials with intriguing optical and electronic properties. This enables applicability in organic electronics and optoelectronics (OLEDs, OFETs, photovoltaics) or as sensory materials.
The potential of our B–C coupling protocol using metal-free catalytic Si/B exchange condensation is demonstrated by the synthesis of a series of π-conjugated monodisperse (het)aryl oligoboranes. Variation of the (het)aryl moieties allowed for tunability of the optoelectronic properties of the materials. Additionally, catalytic C–C cross-coupling strategies were applied to synthesize oligofuryl-based mono- and bisboranes, as well as polymers. These studies led to very robust and highly emissive compounds (f up to 97 %), which allow for tuning of their emission color from blue to orange. Furthermore, this work includes investigations of reaction routes to a kinetically stabilized tetraoxaporphyrinogen.
Being a key aspect of this work, a full investigation of the mechanism of the catalytic Si/B exchange was carried out. Additionally, this work presents the use of borenium cations to perform B–C coupling via intermolecular electrophilic borylation. Similar to the Si/B exchange, this route is capable of giving access to diaryl(bromo)boranes.
Der erste Teil dieser Arbeit beschäftigt sich mit der "Synthese und Reaktivität sterisch anspruchsvoller Iminoborane". Dabei war es möglich, ausgehend von einem Terphenylamin geeignete Aminoborane zu synthetisieren, welche anschließend mit starken, nicht-nukleophilen Basen umgesetzt wurden. Mittels formaler HCl-Eliminierung mit LiTmp gelang auf diese Weise die Darstellung sterisch anspruchsvoller Iminoborane.
Der zweite Teil dieser Arbeit befasst sich mit der "Untersuchung von B-B-Doppelbindungen als Bestandteil konjugierter p-Systeme". Durch die Verwendung von sterisch wenig anspruchsvollen Liganden oder Boryl-Substituenten war es möglich planare Diboren-Systeme zu generieren und darüberhinaus Divinyldiborene darzustellen.
Twisted boron-based biradicals featuring unsaturated C\(_2\)R\(_2\) (R=Et, Me) bridges and stabilization by cyclic (alkyl)(amino)carbenes (CAACs) were recently prepared. These species show remarkable geometrical and electronic differences with respect to their unbridged counterparts. Herein, a thorough computational investigation on the origin of their distinct electrostructural properties is performed. It is shown that steric effects are mostly responsible for the preference for twisted over planar structures. The ground-state multiplicity of the twisted structure is modulated by the σ framework of the bridge, and different R groups lead to distinct multiplicities. In line with the experimental data, a planar structure driven by delocalization effects is observed as global minimum for R=H. The synthetic elusiveness of C\(_2\)R\(_2\)-bridged systems featuring N-heterocyclic carbenes (NHCs) was also investigated. These results could contribute to the engineering of novel main group biradicals.
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.
The synthesis and characterization of Lewis acid/base adducts between tris(pentafluoroethyl)difluorophosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and selected N-heterocyclic carbenes (NHCs) R\(_{2}\)Im (1,3-di-organyl-imidazolin-2-ylidene) and phosphines are reported. For NHCs with small alkyl substituents at nitrogen (R=Me, nPr, iPr) the adducts NHC ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (2 a–h) were isolated. The reaction with the sterically more demanding NHCs Dipp\(_{2}\)Im (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene) (1 i) and tBu\(_{2}\)Im (1,3-di-tert-butyl-imidazolin-2-ylidene) (1 j) afforded the aNHC adducts 3 i and 3 j (a denotes “abnormal” NHC coordination via a backbone carbon atom). The use of tBuMeIm (1-tert-butyl-3-methyl-imidazolin-2-ylidene) (1 m) led to partial decomposition of the NHC and formation of the salt [tBuMeIm−H][MeIm ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)] (4 m). The phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) forms adducts with PMe\(_{3}\) but does not react with PPh\(_{3}\) or PCy\(_{3}\). The mer-cis isomer of literature-known Me\(_{3}\)P ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (5 a) was structurally characterized. Mixtures of the phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and the sterically encumbered NHCs tBu\(_{2}\)Im, Dipp\(_{2}\)Im, and Dipp\(_{2}\)Im\(^{H2}\) (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolidin-2-ylidene) (1 k) showed properties of FLPs (Frustrated Lewis Pairs) as these mixtures were able to open the ring of THF (tetrahydrofuran) to yield NHC−(CH\(_{2}\))\(_{4}\)O−PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) 6 i–k. Furthermore, the deprotonation of the weak C−H acids CH\(_{3}\)CN, acetone, and ethyl acetate was achieved, which led to the formation of the corresponding imidazolium salts and the phosphates [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CN)]\(^{-}\) (7), [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(OC(=CH\(_{2}\))CH\(_{3}\))]\(^{-}\) (8) and [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CO\(_{2}\)Et)]\(^{-}\) (9).
Novel dyes were prepared by simple “click CuAAC” attachment of a triarylborane–alkyne to the azide side chain of an amino acid yielding triarylborane dye 1 which was conjugated with pyrene (dye 2) forming a triarylborane–pyrene FRET pair. In contrast to previous cationic triarylboranes, the novel neutral dyes interact only with proteins, while their affinity to DNA/RNA is completely abolished. Both the reference triarylborane amino acid and triarylborane–pyrene conjugate bind to BSA and the hDPP III enzyme with high affinities, exhibiting a strong (up to 100-fold) fluorescence increase, whereby the triarylborane–pyrene conjugate additionally retained FRET upon binding to the protein. Furthermore, the triarylborane dyes, upon binding to the hDPP III enzyme, did not impair its enzymatic activity under a wide range of experimental conditions, thus being the first non-covalent fluorimetric markers for hDPP III, also applicable during enzymatic reactions with hDPP III substrates.
A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K\(^+\) in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O−H⋅⋅⋅O and O−H⋅⋅⋅N hydrogen bonding, as well as arene-perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.
The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange
(2021)
The dimethyl bismuth cation, [BiMe\(_2\)(SbF\(_6\))], has been isolated and characterized. Reaction with BiMe\(_3\) allows access to the first compound featuring Bi→Bi donor–acceptor bonding. In solution, dynamic behavior with methyl exchange via an unusual S\(_E\)2 mechanism is observed, underlining the unique properties of bismuth species as soft Lewis acids with the ability to undergo reversible Bi−C bond cleavage.
The development of complexes featuring low-valent, multiply bonded metal centers is an exciting field with several potential applications. In this work, we describe the design principles and extensive computational investigation of new organometallic platforms featuring the elusive manganese-manganese bond stabilized by experimentally realized N-heterocyclic carbenes (NHCs). By using DFT computations benchmarked against multireference calculations, as well as MO- and VB-based bonding analyses, we could disentangle the various electronic and structural effects contributing to the thermodynamic and kinetic stability, as well as the experimental feasibility, of the systems. In particular, we explored the nature of the metal-carbene interaction and the role of the ancillary η\(^{6}\) coordination to the generation of Mn\(_{2}\) systems featuring ultrashort metal-metal bonds, closed-shell singlet multiplicities, and positive adiabatic singlet-triplet gaps. Our analysis identifies two distinct classes of viable synthetic targets, whose electrostructural properties are thoroughly investigated.
In recent years, research in the fields of optoelectronics, anion sensors and bioimaging agents have been greatly influenced by novel compounds containing triarylborane motifs. Such compounds possess an empty p‐orbital at boron which results in useful optical and electronic properties. Such a diversity of applications was not expected when the first triarylborane was reported in 1885. Synthetic approaches to triarylboranes underwent various changes over the following century, some of which are still used in the present day, such as the generally applicable routes developed by Krause et al. in 1922, or by Grisdale et al. in 1972 at Eastman Kodak. Some other developments were not pursued further after their initial reports, such as the synthesis of two triarylboranes bearing three different aromatic groups by Mikhailov et al. in 1958. This review summarizes the development of synthetic approaches to triarylboranes from their first report nearly 135 years ago to the present.
The first Borono-Strecker reaction has been developed to synthesize α-aminoboronates via a multicomponent reaction of readily available carbonyl compounds (aldehydes and ketones), amines and B2pin2. The preparation of α-amino cyclic boronates can be achieved via multicomponent coupling of salicylaldehydes, amines, and B2(OH)4. In addition, the diazaborole-based PBP pincer palladium chloride and the diazaborole-based PBP pincer palladium trifluoromethanesulfonate complexes were synthesized and fully characterized for the first time, and used as catalysts for Suzuki-Miyaura cross-coupling reactions.
A novel and convenient methodology for the one-pot synthesis of sterically congested triarylboranes by using bench-stable aryltrifluoroborates as the boron source is reported. This procedure gives systematic access to symmetrically and unsymmetrically substituted triarylboranes of the types BAr\(_{2}\)Ar’ and BArAr'Ar’’, respectively. Three unsymmetrically substituted triarylboranes as well as their iridium-catalyzed C−H borylation products are reported. These borylated triarylboranes contain one to three positions that can subsequently be orthogonally functionalized in follow-up reactions, such as Suzuki-Miyaura cross-couplings or Sonogashira couplings.
An N-heterocyclic-carbene-stabilized diboryne undergoes rapid, high-yielding and catalyst-free hydroamina- tion reactions with primary amines, yielding 1-amino-2-hydro- diborenes, which can be considered boron analogues of enamines. The electronics of the organic substituent at nitrogen influence the structure and further reactivity of the diborene product. With electron-rich anilines, a second hydroamination can occur at the diborene to generate 1,1-diamino-2,2-dihy- drodiboranes. With isopropylamine, the electronic influence of the alkyl substituent upon the diborene leads to an unprece- dented boron-mediated intramolecular N-dearylation reaction of an N-heterocyclic carbene unit.
Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC\(_{6}\)H\(_{4}\))-closo-1,2-C\(_{2}\)B\(_{10}\)H\(_{10}\)-2-)\(_{2}\)(4-MeC\(_{6}\)H\(_{4}\))B] (1), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr\(_{2}\). Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1\(^{.−}\) was isolated and characterized. Single-crystal structure analyses allow an in-depth comparison of 1, 1\(^{.−}\), their calculated geometries, and the S\(_{1}\) excited state of 1. Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD-DFT calculations were used to identify transition-relevant orbitals.
Ein wesentliches Ziel dieser Arbeit war die Durchführung von regioselektiven Deborierungsreaktionen von 1,7-Dicarba-closo-dodecaboranen sowie die Herstellung von polyfunktionalisierten meta-Carboran-Derivaten. Die synthetisierten {nido-7,9-C2B9}- und {closo-1,7-C2B10}-Derivate und ausgewählte ortho-Carboran-Derivate wurden nach erfolgter Kumada-artiger Kreuzkupplungsreaktion bzgl. ihrer Koordinationschemie untersucht. Die ethinylfunktionalisierten Borcluster wurden als Edukte für die Herstellung von Gold(I)-Komplexen genutzt. Weitere Ziele dieser Arbeit waren außerdem die Synthese und umfassende Charakterisierung des gemischten Fluorohydridoborat-Anions [BHF3]− und der carboranylsubstituierten Borat-Anionen [1-HF2B-closo-1,2-C2B10H11]− und [1-HF2B-9,12-I2-closo-1,2-C2B10H9]− sowie die Untersuchung hinsichtlich ihrer Folgechemie.
In der vorliegenden Arbeit wurde die Synthese, Funktionalisierung und Reaktivität von 1,4,2,3-Diazadiborininen untersucht. Zu Beginn sollten Bis(dimethylamino)-substituierte Diazadiborinine mit unterschiedlichen Resten an den Stickstoffatomen dargestellt werden, deren weitere Funktionalisierung später im Fokus stand. Die Synthese erfolgte durch Reduktion von 1,4-Diazabutadienen mit elementarem Lithium und anschließender Salzeliminierungsreaktion mit B2(NMe2)2Cl2. Dadurch ließen sich die monocyclischen vier N,N’-Diaryl-substituierten Diazadiborinine sowie ein Alkyl-substituiertes Diazadiborinin darstellen. Durch etablierte Methoden der Diboran(4)-Chemie wurden diese in ihre Halogenderivate (Cl, Br, I) überführt. Aus diesen konnten drei 2,3-Diazido-1,4,2,3-diazadiborinine durch Umsetzung mit TMSN3 aus den Dihalogenderivaten dargestellt werden. Diese stellen hierbei die ersten isolierten Diboran(4)azidverbindugen dar. Ebenso gelang die Synthese eines bicyclischen Naphthalinisosters, welches erneut erfolgreich in seine Halogenderivate sowie das Diazdidoderivat überführt werden konnte. Einen Einblick in den Mechanismus der 1,4,2,3-Diazadiborininbildung ermöglichte die Isolierung eines Diazadiboretidinintermediats, welches durch doppelte Salzeliminierung entsteht. Dieses erwies sich jedoch als metastabil und lagerte zum Sechsring Diazadiborinin um. Quantenchemische Berechnungen unterstutzten die experimentellen Befunde. Über Kommutierungsreaktionen konnte eine Vielzahl an B,B‘-unsymmetrisch substituierten Diazadiborininen dargestellt und isoliert werden, wobei je nach verwendeten Startmaterialien entweder Gleichgewichtsreaktionen oder quantitative Umsetzungen beobachtet wurden.
Ebenso wurde die Reaktivität der neuartigen Diazidodiborane(4) gegenüber Lewis-Basen untersucht. Sowohl das monocyclische Diazadiborinin, als auch das Benzodiazadiborinin konnten mit NHC-Basen zu den fünf verschiedenen Addukten umgesetzt werden. Unter thermischer Belastung wurde bei den monocyclischen Addukten eine Staudinger-artige Reaktion beobachtet, die unter Freisetzung von N2 zur Bildung von Guanadin-substituierten Diborane(4) führte. Die Benzodiazadiborininaddukte zeigten jedoch eine gänzlich andere Reaktivität. Hier fand eine Ringverkleinerungsreaktion unter Bildung von Diazaborolen statt, welche unter Wanderung einer Azidfunktion auf das NHC-stabilisierte Boratom gebildet wurden. Auf diese Weise konnten drei 1,1-Diamino-2,2-diazidodiborane(5) isoliert werden. Während bei der Umsetzung des Naphtalenderivats mit cAAC keine selektive Reaktion beobachtet wurde, reagierte das monocyclische Diazadiborinin mit zwei Äquivalenten cAAC. Hier bedingte das erste Carbon eine Staudinger-artige Reaktion, die unter Distickstofffreisetzung zu einem Formamidin führte. Die zweite Azidgruppe wurde am $\gamma$-Stickstoffatom von einem weiteren Äquivalent cAAC koordiniert.
In weiteren Reaktivitätsstudien wurde die Generierung von transienten Iminoboranen aus Diazidodiazadiborininen untersucht. Die Diazide zeigten bei Temperaturen von über 150 °C ein sehr selektives Reaktionsverhalten und gingen unter Freisetzung von Distickstoff zu 1,3,2,4-Diazadiboretidin über, wobei dies über die Dimerisierung eines intermediär gebildeten siebengliedrigen, endocyclischen Iminoborans verlief. Der Mechanismus zur Bildung der transienten Iminoborane wurde anhand zweier möglicher Bildungswege mit quantenchemischen Methoden untersucht.
Im letzten Kapitel wurde die Reaktivität des Dihydrodiazadiborinins gegenüber
NHC- und cAAC-Lewis-Basen untersucht. Die Umsetzung mit cAAC führte zu einer B–H-Bindungsaktivierung durch das Carbenkohlenstoffatom, die vermutlich über eine Adduktspezies verläuft. Mit dem gesättigten NHC SIMes wurde ebenfalls keine Adduktbildung beobachtet, auch wenn ein derartiges Intermediat vermutlich durchlaufen wird. Als Produkt der Umsetzung wurde indes ein bicyclisches Molekül identifiziert, welches durch doppelte Ringerweiterung gebildet wurde. Mit ungesättigten NHCs wurden drei Addukte isoliert, welche jedoch nur metastabil waren und beim Erwärmen in bicyclische Verbindungen umlagerten. Die Umlagerungsprodukte konnten weiterhin durch Koordination eines weiteren Äquivalents IMe an die B–H-Funktionalität erneut zu Addukten umgesetzt werden.
Die Bildung der zweier bicyclischer Verbindungen wurde ebenfalls mit quantenchemischen Methoden untersucht, wobei ein vierstufiger Prozess durchlaufen wird. Nach der Bildung des NHC-Addukts erfolgt die Übertragung eines Hydrids auf das Carbenkohlenstoffatom. Durch Insertion eines Boratoms in die NC-Bindung des Carbenrings wird eine Spiroverbindung gebildet und im letzten Schritt folgt die Spaltung der BB-Bindung durch Insertion des ehemaligen Carbenkohlenstoffatoms, was zur Bildung der Bicyclen führt.
Based on the strand‐like coordination polymer (CP) type \(^{1}\)\(_{∞}\)[Ln(BSB)\(_{3}\)(py)\(_{2}\)], [BSB]−=bis‐salicylatoborate anion, mixed Eu/Tb‐containing compounds of the constitution \(^{1}\)\(_{∞}\)[Eu\(_{x}\)Tb\(_{1-x}\)(BSB)\(_{3}\)(py)\(_{2}\)] were synthesised ionothermally for a phase width of (x=0.25–0.75) and characterized regarding structure and optical properties. Previously, known only for other lanthanides, the mixed 1D−Eu/Tb‐CPs show excellent options for statistic replacement of the Ln‐cations during synthesis yielding solid solutions. The products are highly luminescent, with the chromaticity being a direct function of the amount of the respective Ln‐ions. Corresponding to an overall addition of emission intensities, the green Tb\(^{3+}\) emission and the red Eu\(^{3+}\) emission allow for a chromaticity control that also includes yellow emission. Control of the luminescence colour renders them suitable examples of the versatility of statistic replacement of metal ions in coordination chemistry. In addition, crystallization of [EMIm]\(_{2}\)[YCl\(_{5}\)(py)] illuminates possible other products of the ionothermal reactions of [EMIm][BSB] with LnCl\(_{3}\) constituted by components not being part of the main CPs.
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.