Welcome to this themed issue of Dalton Transactions entitled ‘Fluorine’.
Gold trifluoromethyl complexes
This Perspective reviews the synthesis, structure, reactivity and applications of gold trifluoromethyl complexes. The recently reported reactions of gold(III) trifluoromethyl complexes with potential application in synthesis are discussed.
The non-aqueous fluorolytic sol–gel synthesis of nanoscaled metal fluorides
Nanoscopic metal fluorides with new applications.
Chemo-, regio-, and stereo-selective perfluoroalkylations by a Grignard complex with zirconocene
The unique reactivity and high selectivity of the zirconocene-hybridized heterobimetallic perfluoalkyl Grignard reagents can be employed for efficient and highly selective nucleophilic perfluoroalkylation of carbonyl compounds and epoxides, in particular.
Catalytic defluorinative [3 + 2] cycloaddition of trifluoromethylalkenes with alkynes via reduction of nickel(II) fluoride species
A catalytic synthesis of 2-fluoro-1,3-cyclopentadienes was achieved via [3 + 2] cycloaddition of 2-trifluoromethyl-1-alkenes and alkynes using a nickel catalyst and a diboron-based ternary additive system.
Reactions of allyl alcohols and boronic acids with trifluoromethanesulfonyl hypervalent iodonium ylide under copper-catalysis
Trifluoromethylsulfinyl 3 and trifluoromethylthio 5 compounds are independently obtained by using the sulfone-type reagent 1 under Cu catalysis.
Synthesis and optical properties of subphthalocyanine homo- and heterodimers axially connected via a hydroquinone linker
The electron transfer process between subphthalocyanines differs depending on the o-, m-, and p-geometries of the hydroquinone linker.
Organotrifluoroborates as attractive self-assembling systems: the case of bifunctional dipotassium phenylene-1,4-bis(trifluoroborate)
A multitude of non-covalent interactions, investigated by X-ray crystallography and computational chemistry techniques, proved to be responsible of the spontaneous self-assembly of a bis(trifluoroborate) dipotassium salt.
Accessing perfluoroalkyl nickel(II), (III), and (IV) complexes bearing a readily attached [C4F8] ligand
The [C4F8] ligand supports a family of related fluoroalkyl nickel complexes spanning the +2 to +4 oxidation states.
Supramolecular aggregation of Ni(salen) with (C6F5)2Hg and [o-C6F4Hg]3
Organomercurials (C6F5)2Hg and [o-C6F4Hg]3 interact with Ni(II)-salen to form adducts held by arene-perfluoroarene and hydrogen bonding interactions, as well as interactions between Hg, the salen ligand, and Ni.
A combined quantum-chemical and matrix-isolation study on molecular manganese fluorides
Molecular manganese fluorides were studied in solid neon, argon and fluorine using IR spectroscopy and quantum-chemical calculations at DFT and CCSD(T) levels.
A fluorosurfactant and photoreducible CuII-tren click catalyst: surfactant and catalytic properties at liquid/liquid interfaces
The fluorous copper(II)-tren complex 2 is a powerful surfactant which strongly reduces the perfluorodecalin/water and diisopropyl ether/water interface tensions. When photoreduced by light it catalyzes the Huisgen click cycloaddition.
Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds
Synthesis of perfluoroorgano copper lithium and silver couples.
Functionalization of Zr-based MOFs with alkyl and perfluoroalkyl groups: the effect on the water sorption behavior
The influence of organic functional groups (fluorinated versus non-fluorinated) on the hydrophilic/hydrophobic balance of MOFs has been studied.
Iron-catalyzed electrochemical C–H perfluoroalkylation of arenes
A new iron-catalyzed reaction for the coupling of perfluoroalkyl iodides with aromatic substrates is described.
Optimisation of a sol–gel synthesis route for the preparation of MgF2 particles for a large scale coating process
Preparation of transparent and low viscous MgF2 sols via sol–gel technique which can be applied for antireflective coatings on glass substrates is described.
Brønsted acid-promoted C–F bond activation in [P,S]-ligated neutral and anionic perfluoronickelacyclopentanes
Bidentate phosphinothiol ligand induces C–F bond functionalization in perfluoronickelacycles.
Structure investigations on oxygen fluorides
The solid state structures of O2F2 and OF2 resemble those in the gaseous state. Attempts to isolate the proposed (O2+)2PdF62− from O2F in HF result in the formation of (O2+H3Pd2F12−)n.
Transition metal complexes bearing NHC ligands substituted with secondary polyfluoroalkyl groups
Silver and palladium complexes bearing dihydroimidazolylidene or imidazolidinylidene NHC ligands substituted with racemic secondary polyfluoroalkyl groups were synthesized.
Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand
Fluorination reactions at platinum(0) alkyne complexes with N-fluorobenzenesulfonimide (NFSI) occur either at the metal centre or at the metal bound alkyne to give β-fluorovinyl complexes.
The structure of trimethyltin fluoride
Contrary to previous reports, trimethyltin fluoride was shown to adopt a linear chain structure with symmetric fluorine bridges in the solid state.
Isocyanate deinsertion from κ1-O amidates: facile access to perfluoroaryl rhodium(I) complexes
Perfluorophenyl-subsituted amidates undergo unprecedented C6F5 migration to Rh(I) on heating, providing a new route to Rh-C6F5 organometallic fragments.
Salts of highly fluorinated weakly coordinating anions as versatile precursors towards hydrogen storage materials
Metathetic reactions using salts of highly-fluorinated weakly coordinating anions permit synthesis of high-purity hydrogen storage materials.
Highly electron-poor Buchwald-type ligand: application for Pd-catalysed direct arylation of thiophene derivatives and theoretical consideration of the secondary Pd0–arene interaction
Highly electron-poor SPhos ligands stabilised the Pd complex by secondary Pd0–arene interaction.
Phase and redox shifted four iron/four sulfur clusters: fluorous analogs of metalloenzyme cofactors
The title compounds, [Q]2[Fe4S4(S(CH2)nRf8)4], feature dianions with four fluorous thiolate ligands and cations that are non-fluorous, “light fluorous”, or “heavy fluorous”; fluorous/organic partition coefficients can reach >93 : <7.
Perfluoropropenyl-containing phosphines from HFC replacements
From HFC replacements CF3CF2CH2F and Z-CF3CFCFH new E-perfluoropropenyl phosphine ligands are prepared, including the first perfluoroalkenyl bidentate phosphine, (E-CF3CFCF)2PCH2CH2(E-CFCFCF3)2.
What causes the weakest host to act as the strongest one? A theoretical study on the host–guest chemistry of five azacryptands and fluoride anions
Among five studied hosts, the one having the lowest attractive interaction with a fluoride anion shows the highest selectivity in solution due to reduced solvent hindrance.
Fluoride solid electrolytes: investigation of the tysonite-type solid solutions La1−xBaxF3−x (x < 0.15)
La1−xBaxF3−x solid solutions for x < 0.15 were prepared by solid state synthesis in a platinum tube under an nitrogen atmosphere with subsequent quenching for 0.07 ≤ x < 0.15.
AgPO2F2 and Ag9(PO2F2)14: the first Ag(I) and Ag(I)/Ag(II) difluorophosphates with complex crystal structures
Detailed characterization is presented of novel AgPO2F2 and AgI4AgII5(PO2F2)14 salts including their complex crystal structures and thermal decomposition.
Brønsted acid-catalyzed 1,2-fluorine migration with fluoroepoxides
An efficient 1,2-fluorine migration reaction was realized under Brønsted acid catalysis in the absence of an external fluorinating source. The high fluorine atom economy and very mild conditions make this reaction a promising protocol for the construction of the C–F bond.
Synthesis, structure, and reactivity of iridium perfluorocarbene complexes: regio- and stereo-specific addition of HCl across a metal carbon double bond
Addition of HCl to perfluorocarbene complexes of iridium occurs regiospecifically and stereospecifically.
C–F sp2 bond functionalization mediated by niobium complexes
The functionalization of fluorobenzene is described via insertion of isocyanide after the oxidative addition of the C–F bond.
Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)
Multiple catalytic hydrodefluorination steps take place with the trans-dihydride complex [Ru(IEt2Me2)2(PPh3)2H2] (1), taking C6F6 to tri-, di- and mono-fluorobenzenes.
Axial fluoride binding by lanthanide DTMA complexes alters the local crystal field, resulting in dramatic spectroscopic changes
Dramatic changes are observed in both the NMR and luminescence spectra of LnDTMA complexes on addition of fluoride, consistent with a change in the nature of the magnetic anisotropy at the paramagnetic lanthanide centre.
Kinetico-mechanistic studies on the formation of seven-membered [C,N]-platinacycles: the effect of methyl or fluoro substituents on the aryl ancillary ligands
The rate determining step for the formation of seven-membered platinacycles from cyclometallated Pt(IV) aryl complexes is determined by the nature of the substituents on the aryl groups.
Synthesis of new asymmetric substituted boron amidines – reactions with CO and transfer hydrogenations of phenylacetylene
Formation of amidine–BH(C6F5)2 adducts and their thermal dehydrogenation, CO uptake to form five-membered cyclic compounds and stoichiometric transfer hydrogenation toward phenylacetylene.
Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron
The three isoelectronic inner salts 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2) are accessible by fluorination of x-H3N-closo-1-CB11H11 (x = 12, 2) and 7-H3N-12-F-closo-1-CB11H10, respectively. Deprotonation of the decafluorinated ammoniocarba-closo-dodecaboranes yields the corresponding aminocarba-closo-dodecaborate anions [1-H-x-H2N-closo-1-CB11F10]− (x = 12, 7, 2).
A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp3 α, β, and γ carbon–fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes
Inner-sphere reduction of a (pentafluoroethyl)(trifluoromethyl)carbene ligand affords perfluorobutyne, perfluorobutatriene and perfluorometallacyclobutene ligands.
P-Trifluoromethyl ligands derived from Josiphos in the Ir-catalysed hydrogenation of 3,4-dihydroisoquinoline hydrochlorides
Ferrocenyl phosphines containing a stereogenic P-CF3 group show improved selectivities in the Ir-catalysed hydrogenation of dihydroisoquinolinium derivatives.
Aryl-BIAN-ligated silver(I) trifluoromethoxide complex
The complex (Aryl-BIAN)AgOCF3 has been synthesised and structurally characterised. The reactivity towards trifluoromethoxylation of benzyl bromides has also been examined.
About this collection
Guest Edited by Professor Jennifer Love (University of British Columbia), this issue focuses on all applications of fluorine in inorganic chemistry, including: organometallic and coordination complexes using fluorinated ligands, metal-catalysed and metal-mediated fluorination and C–F activation reactions, main group fluoride compounds, solid state metal fluorides, molecular fluoride complexes and materials for fluoride sensing and anion binding.