Themed collection Fluorine

Welcome to this themed issue of Dalton Transactions entitled ‘Fluorine’.

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.

Nanoscopic metal fluorides with new applications.

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.

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.

Trifluoromethylsulfinyl 3 and trifluoromethylthio 5 compounds are independently obtained by using the sulfone-type reagent 1 under Cu catalysis.

The electron transfer process between subphthalocyanines differs depending on the o-, m-, and p-geometries of the hydroquinone linker.

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.

The [C₄F₈] ligand supports a family of related fluoroalkyl nickel complexes spanning the +2 to +4 oxidation states.

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.

Molecular manganese fluorides were studied in solid neon, argon and fluorine using IR spectroscopy and quantum-chemical calculations at DFT and CCSD(T) levels.

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.

Synthesis of perfluoroorgano copper lithium and silver couples.

The influence of organic functional groups (fluorinated versus non-fluorinated) on the hydrophilic/hydrophobic balance of MOFs has been studied.

A new iron-catalyzed reaction for the coupling of perfluoroalkyl iodides with aromatic substrates is described.

Preparation of transparent and low viscous MgF₂ sols via sol–gel technique which can be applied for antireflective coatings on glass substrates is described.

Bidentate phosphinothiol ligand induces C–F bond functionalization in perfluoronickelacycles.

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.

Silver and palladium complexes bearing dihydroimidazolylidene or imidazolidinylidene NHC ligands substituted with racemic secondary polyfluoroalkyl groups were synthesized.

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.

Contrary to previous reports, trimethyltin fluoride was shown to adopt a linear chain structure with symmetric fluorine bridges in the solid state.

Perfluorophenyl-subsituted amidates undergo unprecedented C₆F₅ migration to Rh(I) on heating, providing a new route to Rh-C₆F₅ organometallic fragments.

Metathetic reactions using salts of highly-fluorinated weakly coordinating anions permit synthesis of high-purity hydrogen storage materials.

Highly electron-poor SPhos ligands stabilised the Pd complex by secondary Pd⁰–arene interaction.

The title compounds, [Q]₂[Fe₄S₄(S(CH₂)_nR_f8)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.

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.

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.

La_1−xBa_xF_3−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.

Detailed characterization is presented of novel AgPO₂F₂ and Ag^I₄Ag^II₅(PO₂F₂)₁₄ salts including their complex crystal structures and thermal decomposition.

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.

Addition of HCl to perfluorocarbene complexes of iridium occurs regiospecifically and stereospecifically.

The functionalization of fluorobenzene is described via insertion of isocyanide after the oxidative addition of the C–F bond.

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.

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.

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.

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.

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).

Inner-sphere reduction of a (pentafluoroethyl)(trifluoromethyl)carbene ligand affords perfluorobutyne, perfluorobutatriene and perfluorometallacyclobutene ligands.

Ferrocenyl phosphines containing a stereogenic P-CF₃ group show improved selectivities in the Ir-catalysed hydrogenation of dihydroisoquinolinium derivatives.

The complex (Aryl-BIAN)AgOCF₃ has been synthesised and structurally characterised. The reactivity towards trifluoromethoxylation of benzyl bromides has also been examined.