Themed collection Spotlight Collection: Fluorinated ligands

36 items
Editorial

Fluorinated ligands and their effects on physical properties and chemical reactivity

Guest Editors Linda H. Doerrer and Rasika Dias introduce the spotlight collection: “Fluorinated ligands and their effects on physical properties and chemical reactivity”.

Graphical abstract: Fluorinated ligands and their effects on physical properties and chemical reactivity
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

Never a dull moment with praseodymium metal

[BiI2(DippForm)2], [BiII2(DippForm)2(C6F5)2] [BiIII(DippForm)2(C6F5)], [Pr(DippForm)2F(thf)]·PhMe, [p-HC6F4DippForm]·0.5thf, and a ring-opened thf [o-HC6F4O(CH2)4DippForm] were obtained by the reaction of Pr metal with [Bi(C6F5)3]·0.5dioxane, DippFormH in thf.

Graphical abstract: Never a dull moment with praseodymium metal
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

Probing B–X to B–H conversions and applications in C–F bond activation catalysis

The conversion of B–X to B–H bonds in the presence of silane is probed. 9-X-9-borabicyclo[3.3.1]nonane (B–F-9-BBN, = F) is shown to react directly with silane. Thus 9-BBN in the presence of silane catalyzes benzylation of arenes with benzyl fluorides.

Graphical abstract: Probing B–X to B–H conversions and applications in C–F bond activation catalysis
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

Fluorinated tris(pyridyl)borate ligand support on coinage metals

Chemically robust, tris(pyridyl)borate with a fluorine-lined coordination pocket allows the stabilization and detailed investigation of organometallic complexes of group 11 metal ions involving a small gaseous molecule, ethylene.

Graphical abstract: Fluorinated tris(pyridyl)borate ligand support on coinage metals
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

Impact of successive fluorinations onto redox, spectroscopic and NMR properties of ferrocene.

Graphical abstract: From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

C–H and C–F coordination of arenes in neutral alkaline earth metal complexes

A series of neutral magnesium and calcium complexes that display various novel group 2⋯arene interaction have been synthesised and structurally characterised.

Graphical abstract: C–H and C–F coordination of arenes in neutral alkaline earth metal complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Communication

Isolation and structural characterisation of rhodium(III) η2-fluoroarene complexes: experimental verification of predicted regioselectivity

Well defined rhodium complexes for probing the coordination site preference of partially fluorinated benzenes.

Graphical abstract: Isolation and structural characterisation of rhodium(iii) η2-fluoroarene complexes: experimental verification of predicted regioselectivity
From the themed collection: Spotlight Collection: Fluorinated ligands
Communication

Direct conversion of uranium dioxide UO2 to uranium tetrafluoride UF4 using the fluorinated ionic liquid [Bmim][PF6]

[Bmim][PF6] ionic liquid is used for the direct conversion of uranium dioxide UO2 to uranium tetrafluoride UF4.

Graphical abstract: Direct conversion of uranium dioxide UO2 to uranium tetrafluoride UF4 using the fluorinated ionic liquid [Bmim][PF6]
From the themed collection: Spotlight Collection: Fluorinated ligands
Accepted Manuscript - Paper

Coinage metal-ethylene complexes of sterically demanding 1,10-phenanthroline ligands

From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Interplay between coordination sphere engineering and properties of nickel diketonate–diamine complexes as vapor phase precursors for the growth of NiO thin films

Coordination sphere engineering of nickel diketonate–diamine adducts enables tailoring of precursor properties of relevance for the vapor phase deposition of pure NiO films.

Graphical abstract: Interplay between coordination sphere engineering and properties of nickel diketonate–diamine complexes as vapor phase precursors for the growth of NiO thin films
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Anionic N-heterocyclic carbenes featuring weakly coordinating perfluoroalkylphosphorane moieties

Novel anionic N-heterocyclic carbenes featuring weakly coordinating (C2F5)3PF2 groups at imidazoline were synthesized. These WCA-NHCs are promising ligands with enhanced donor and acceptor properties compared to neutral NHCs.

Graphical abstract: Anionic N-heterocyclic carbenes featuring weakly coordinating perfluoroalkylphosphorane moieties
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Fluorinated linkers enable the synthesis of flexible MOFs with 1D alkaline earth SBUs and a temperature-induced phase transition

The use of fluorinated BTB leads to the formation of UoC-9 with an unprecedented framework topology, crystalline sponge behaviour and a low-temperature phase transition. Hirshfeld analysis reveals the underlying host–guest interactions in this MOF.

Graphical abstract: Fluorinated linkers enable the synthesis of flexible MOFs with 1D alkaline earth SBUs and a temperature-induced phase transition
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

An investigation into the Brønsted acidity of the perfluorinated alkoxy silanes {(F3C)3CO}3SiH and {(F6C5)3CO}2Si(Cl)H

The Si–H bond in {(F3C)3CO}3SiH is exceptionally strong and short; yet the acidity is comparable to common organic acids. This apparent contradiction will be discussed with the aid of contemporary DFT methods.

Graphical abstract: An investigation into the Brønsted acidity of the perfluorinated alkoxy silanes {(F3C)3CO}3SiH and {(F6C5)3CO}2Si(Cl)H
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Substitution lability of the perfluorinated Cp* ligand in Rh(I) complexes

Fluorinated pyridines can displace the anionic [C5(CF3)5] ligand in [Rh(COD)(C5(CF3)5)], however the reaction is reversible in weakly coordinating solvents as CHCl3.

Graphical abstract: Substitution lability of the perfluorinated Cp* ligand in Rh(i) complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Synthesis of imidazolium-based pentacoordinated organofluorosilicate and germanate salts

Naked fluoride reagent [IPrH][F] was used to prepare and structurally characterise a rare organofluorogermanate compound [IPrH][Ph3GeF2] and other organofluorosilicate species.

Graphical abstract: Synthesis of imidazolium-based pentacoordinated organofluorosilicate and germanate salts
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Phenylimido complexes of rhenium: fluorine substituents provide protection, reactivity, and solubility

The electronic properties and steric bulk of isocyanides are modulated by partial fluorination of the ligands. The fluorination of phenylimides provides solubility.

Graphical abstract: Phenylimido complexes of rhenium: fluorine substituents provide protection, reactivity, and solubility
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications

Dream WCA…? The very high fluoride ion affinity of the Lewis acid underlying the novel WCA [Al(OC10F15)4] ([pfAd]) nurtures the hope for having found a new “dream WCA”. Yet, the paths towards this WCA held some obstacles at hand...!

Graphical abstract: The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu(I) pyrazolate cyclotrimers

Cu3[4-I-3,5-(CF3)2Pz]3 exhibits stronger supramolecular Cu3⋯halogen interactions vs. its 4-Br/4-Cl analogues, double- vs. single-capped; this relativistic enhancement yet results in quenched phosphorescence.

Graphical abstract: Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu(i) pyrazolate cyclotrimers
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Synthesis and lewis acidity of fluorinated triaryl borates

A series of fluorinated triaryl borates B(OArF)3 (ArF = 2-FC6H4, 3-FC6H4, 4-FC6H4, 2,4-F2C6H3, 3,5-F2C6H3, 2,3,4-F3C6H2, 2,4,6-F3C6H2, 3,4,5-F3C6H2) have been prepared and isolated from the reactions of the mono-, di-, or tri-fluorophenol with BCl3.

Graphical abstract: Synthesis and lewis acidity of fluorinated triaryl borates
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand

Novel coordination chemistry of iridium(I) and iridium(III) using a trifluoromethyl-functionalised PONOP pincer ligand.

Graphical abstract: Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Reactivity of bi- and monometallic trifluoroacetates towards amorphous SiO2

The reactivity of alkali–manganese(II) and alkali trifluoroacetates towards amorphous SiO2 was studied in the solid-state with an eye towards the synthesis of alkali fluorosilicates.

Graphical abstract: Reactivity of bi- and monometallic trifluoroacetates towards amorphous SiO2
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(II) and cobalt(II) complexes

A fluorophenyl-substituted ligand drives complete and partial spin-crossover in Fe(II) and Co(II) complexes, respectively.

Graphical abstract: Fluorinated click-derived tripodal ligands drive spin crossover in both iron(ii) and cobalt(ii) complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Synthesis, structure, and electrochemical properties of [LNi(Rf)(C4F8)] and [LNi(Rf)3] complexes

The new anionic nickelate complexes [(MeCN)Ni(C4F8)(CF3)], [(MeCN)Ni(C4F8)(C2F5)], [(IMes)Ni(C4F8)(CF3)], [(IMes)Ni(CF3)3] and [(F-NHC)Ni(Rf)3] (F-NHC = fluorinated NHC) were synthesized and fully characterized.

Graphical abstract: Synthesis, structure, and electrochemical properties of [LNi(Rf)(C4F8)]− and [LNi(Rf)3]− complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Open Access Paper

Oxidation of europium with ammonium perfluorocarboxylates in liquid ammonia: pathways to europium(II) carboxylates and hexanuclear europium(III) fluoridocarboxylate complexes

This work introduces the first europium(II) perfluorocarboxylate and the use of its class of compounds in the facile synthesis of octahedro-hexanuclear europium(III) fluoridocarboxylates with interesting luminophoric properties.

Graphical abstract: Oxidation of europium with ammonium perfluorocarboxylates in liquid ammonia: pathways to europium(ii) carboxylates and hexanuclear europium(iii) fluoridocarboxylate complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Lewis acid–base adducts of Al(N(C6F5)2)3 and Ga(N(C6F5)2)3 – structural features and dissociation enthalpies

Herein we present the molecular structures of six neutral Lewis acid–base adducts of the Lewis superacid Al(N(C6F5)2)3 and its higher homolog Ga(N(C6F5)2)3 with the electron pair donors MeCN, CNtBu, THF and PMe3.

Graphical abstract: Lewis acid–base adducts of Al(N(C6F5)2)3 and Ga(N(C6F5)2)3 – structural features and dissociation enthalpies
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Synthesis, structural and photophysical properties of dimethylphosphino(perfluoro-)phenylene-based gold(I) dimers

Driven by different weak non-covalent interactions [Au22-C6H4PMe2)2] and its aryl-perfluorinated analogue aggregate vastly differently in the solid state: the non-fluorinated prefers aurophilic interactions, the fluorinated aryl–aryl interactions.

Graphical abstract: Synthesis, structural and photophysical properties of dimethylphosphino(perfluoro-)phenylene-based gold(i) dimers
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Spin-state control of cobalt(II) and iron(II) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions

Fluorine-specific interactions in the secondary coordination sphere of iron(II) and cobalt(II) complexes with click-derived fluorinated tripodal ligands are shown to control the spin states of the metal centers.

Graphical abstract: Spin-state control of cobalt(ii) and iron(ii) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Facile preparation of a cobalt diamine diketonate adduct as a potential vapor phase precursor for Co3O4films

A novel heteroleptic Co(II) complex has been synthesized, characterized and successfully evaluated as a precursor for the CVD of Co3O4 thin films with tailored properties.

Graphical abstract: Facile preparation of a cobalt diamine diketonate adduct as a potential vapor phase precursor for Co3O4films
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

High magnetization reversal barriers in luminescent dysprosium octahedral and pentagonal bipyramidal single-molecule magnets based on fluorinated alkoxide ligands

Three luminescent single-molecules magnets based on different fluorinated alkoxide ligands and exhibiting high magnetization reversal barriers are reported.

Graphical abstract: High magnetization reversal barriers in luminescent dysprosium octahedral and pentagonal bipyramidal single-molecule magnets based on fluorinated alkoxide ligands
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Investigation of the biological and photophysicochemical properties of new non-peripheral fluorinated phthalocyanines

The photophysicochemical and biological properties of new fluorinated phthalocyanines were examined. The synergistic effect of phthalocyanines used as colorants in ink formulas with other chemicals available was investigated for the first time.

Graphical abstract: Investigation of the biological and photophysicochemical properties of new non-peripheral fluorinated phthalocyanines
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Alkaline-earth complexes with macrocyclic-functionalised bis(phenolate)s and bis(fluoroalkoxide)s

The syntheses and structural features of several families of well-defined complexes of the large alkaline earths (calcium, strontium and barium) bearing dianionic, multidentate bis(phenolato) or bis(fluoroalkoxo) ligands are presented.

Graphical abstract: Alkaline-earth complexes with macrocyclic-functionalised bis(phenolate)s and bis(fluoroalkoxide)s
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Electronic effect of a perfluorinated β-diketiminate ligand on the bonding nature of copper carbonyl complexes

A combined experimental and computational study demonstrates the influence of fluorine substituents on the electronic properties of β-diketiminate ligands.

Graphical abstract: Electronic effect of a perfluorinated β-diketiminate ligand on the bonding nature of copper carbonyl complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Using frustrated Lewis pairs to explore C–F bond activation

Our interest in C–F bond activation prompted an investigation of the reactions of PhC(O)CF3 with a superbasic proazaphosphatrane (Verkade's base) and a corresponding FLP.

Graphical abstract: Using frustrated Lewis pairs to explore C–F bond activation
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes

Reactions of various Rh(I) complexes towards penta-fluorostyrene or its borylated derivative afforded coordination and C–F bond or C–H bond activation reactions.

Graphical abstract: C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Acetylene and terminal alkyne complexes of copper(I) supported by fluorinated pyrazolates: syntheses, structures, and transformations

A variety of isolable, 2 : 1 and 1 : 1 copper(I)–alkyne complexes of containing pyrazolate ligand supports are presented as well as the copper pyrazolate mediated acetylenic C–H and alkyne C[triple bond, length as m-dash]C bond functionalizations.

Graphical abstract: Acetylene and terminal alkyne complexes of copper(i) supported by fluorinated pyrazolates: syntheses, structures, and transformations
From the themed collection: Spotlight Collection: Fluorinated ligands
Paper

Highly fluorinated metal complexes as dual 19F and PARACEST imaging agents

Highly fluorinated, water-soluble transition metal complexes serve as both 19F and PARACEST magnetic resonance imaging agents.

Graphical abstract: Highly fluorinated metal complexes as dual 19F and PARACEST imaging agents
From the themed collection: Spotlight Collection: Fluorinated ligands
36 items

About this collection

Fluorinated ligands and their effects on physical properties and chemical reactivity

Fluorine embodies reactivity and inertness, both of which are exploited by inorganic chemists. It is the most electronegative element in the periodic table (3.98 on the Pauling scale) and has a remarkably high reduction potential (2.87 V).  The van der Waals and covalent radii of fluorine are quite short (ranked third, only after the first-row elements hydrogen and helium), making it unusually small for its atomic number. The homonuclear bond in F2 is particularly reactive while some heteronuclear bonds involving fluorine are remarkably stable. The combined effects of these features on fluorine-containing molecules are often unmatched by any other element, for example with carbon, where it forms very robust, chemically inert single bonds; the BDE of C-F compared to C-H bonds in CF4 and CH4 are 546.8 and 439.3 kJ/mol, respectively. 

Metal complexes of fluorinated ligands in comparison to their non-fluorinated, hydrocarbon counterparts, usually display different properties such as relatively high thermal and oxidative stability, volatility, diminished vibrational modes and shifted spectroscopic features (absorption and emission), as well as unique reactivity profiles. They are also ideal for applications in fluorous-biphase media and supercritical CO2. Additionally, fluorine containing anions such as [BF4]-, [SbF6]-, [B(C6F5)4], and [B{3,5-(CF3)2C6H3}4]are among the weakest donors known. This Spotlight collection brings together contributions by leading researchers on this topic to highlight some of the fascinating developments in fluorinated supporting ligands, C-F inertness, electron-withdrawing effects of fluoro-substituents, the weakly-coordinating nature of fluorinated anions, efforts to functionalize C-F bonds, and species that selectively deliver F, F· and F-.

This collection is guest edited by Dalton Transactions Advisory Board member Professor Rasika Dias, The University of Texas at Arlington, USA, and Professor Linda Doerrer, Boston University, USA.

Articles will be added to this themed collection as soon as possible after they are published. Please return to this page frequently to see the collection grow.

If you would like to contribute an article to this collection, please contact the Editorial Office at dalton-rsc@rsc.org with your proposed topic.

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