Direct Defluorination and Amination of Polytetrafluoroethylene and Other Fluoropolymers by Lithium Alkylamides.

Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and some fluoropolymers such as polyvinylidene fluoride (PVDF) and Nafion by lithium alkylamide salts. Synthesizing these reactants extemporaneously between lithium metal and an aliphatic primary di- or triamine that also serves as a solvent leads to the rapid nucleophilic substitution of fluoride by an alkylamide moiety when in contact with the fluoropolymer. Moreover, lithium alkylamides dissolved in suitable solvents other than amines can react with fluoropolymers. This highly efficient one-pot process opens the way for further surface or bulk modification if needed, providing an easy, inexpensive, and fast experiment protocol on large scales.

Molecular engineering of 3-arylated tetrazo[1,2-b]indazoles: divergent synthesis and structure-property relationships.

The synthetic scope of 3-arylated tetrazo[1,2-b]indazoles is reported based on a Pd-catalyzed Liebeskind-Srogl cross-coupling reaction followed by an N-cyclisation process. The reactivity of the nitrogen atoms was used to further diversify these N-rich polyaromatic tetrazo[1,2-b]indazoles in a panel of reactions (protonation, selective oxidation, metallations). Selective ortho-C-H activation/functionalization on the heterocycle was also demonstrated with three transition metals (TM = Pd, Ir and Rh). The effects of all these molecular engineering strategies, particularly the N-modifications, on the optical and redox properties of the 3-arylated tetrazoindazoles were studied experimentally and theoretically. This study highlights the diversity of molecular structures and electronic properties offered by the tetrazo[1,2-b]indazole platform.

Crystal structure of di-benzyl-ammonium hydrogen (4-amino-phen-yl)arsonate monohydrate.

The title salt, C14H16N+·C6H7AsNO3 -·H2O or [(C6H5CH2)2NH2][H2NC6H4As(OH)O2]·H2O, (I), was synthesized by mixing an aqueous solution of (4-amino-phenyl)-arsonic acid with an ethano-lic solution of di-benzyl-amine at room temperature. Compound I crystallizes in the monoclinic P21/c space group. The three components forming I are linked via N-H⋯O and O-H⋯O inter-molecular hydrogen bonds, resulting in the propagation of an infinite zigzag chain. Additional weak inter-actions between neighbouring chains, such as π-π and N-H⋯O contacts, involving phenyl rings, -NH2 and -As(OH)O3 functions, and H2O, respectively, lead to a three-dimensional network.

Synthesis of meso,ß-Fused Thiazinamine-Porphyrins via Oxidative C-N Fusion of Pyrimidinyl-Substituted Porphyrins.

5,15-Bis(pyrimidin-2-ylthio)porphyrins have been synthesized. Their electrochemical oxidation leads to the formation of mono- and bis-C-N-fused thiopyrimidinium intermediates depending on the applied charge and potential. These latter undergo nucleophilic attack with water during workup that drives the ring opening of the pyrimidinium moiety. When piperidine is added before or after workup, the neutral fused porphyrinthiazin-2-amines are generated, and they exhibit a significant bathochromic shift of their Soret and Q bands.

Tetrazo[1,2-b]indazoles: Straightforward Access to Nitrogen-Rich Polyaromatics from s-Tetrazines.

The straightforward access to a new class of aza-polyaromatics is reported. Starting from readily available fluorinated s-tetrazine, a cyclization process with azide leads to the formation of an unprecedented tetrazo[1,2-b]indazole or a bis-tetrazo[1,2-b]indazole (cis and trans conformers). Based on the new nitrogen core, further N-directed palladium-catalyzed ortho-C-H bond functionalization allows the introduction of halides or acetates. The physicochemical properties of these compounds were studied by a joint experimental/theoretical approach. The tetrazo[1,2-b]indazoles display solid-state π-stacking, low reduction potential, absorption in the visible range up to the near-infrared, and intense fluorescence, depending on the molecular structure.

Hybrid Phosphine/Amino-Acid Ligands Built on Phenyl and Ferrocenyl Platforms: Application in the Suzuki Coupling of o-Dibromobenzene with Fluorophenylboronic Acid.

We describe the synthesis and characterization of two classes of hybrid phosphino ligands functionalized with amino ester or amino acid groups. These compounds are built either on a rigid planar phenyl platform or on a functionalized - conformationally controlled - rotational ferrocene backbone. Modifications at the -PR2 phosphino groups (R=aryl and alkyl, with various steric bulk, Ph, Mes, i-Pr, Cy) and at the amino acid/amino ester functions are reported, showing a valuable high modularity. The coordination chemistry of these compounds regarding palladium and gold was investigated, in particular with respect to the coordination mode of the phosphino groups and the preferred interaction with metals for the amino ester and amino acid functions. For all the hybrid ligands, based either on ferrocenyl or phenyl platforms, the (P,N)-chelating effect dominates in solution for coordination to Pd(II), while linear P-Au(I) complexes without interaction with the amino groups are assumed. The investigation of the catalytic activity of these new ligands in the demanding palladium-catalyzed Suzuki-Miyaura coupling of o-dibromoarenes with fluorophenylboronic acid underlined the importance of the amino ester dicyclohexylphosphinoferrocene for avoiding the deleterious homocoupling and arene oligomerization side-reactions that were otherwise observed with the other phosphine ligands.

Crystal structure of the monoglycidyl ether of isoeugenol.

The title compound, C13H16O3 [GE-isoEu; systematic name: 2-({2-meth-oxy-4-[(E)-1-propen-1-yl]phen-oxy}meth-yl)oxirane], which crystallizes in the triclinic P space group, was synthesized in one step from iso-eugenol, a bio-based phenyl-propanoid, with an excess of epi-chloro-hydrin. Colourless prismatic crystals suitable for X-ray diffraction were obtained from a mixture of ethyl acetate and cyclo-hexane, during purification by column chromatography on silica gel. GE-isoEu, which corresponds to the trans isomer of the monoglycidyl ether of iso-eugenol, is based on a 1,2,4-tris-ubstituted benzene ring by diglycidyl ether, meth-oxy and 1-(E)-propenyl groups, respectively. In the crystal, mol-ecules are organized through offset π-stacking inter-actions. Chemically, GE-isoEu constitutes an inter-mediate in the synthesis protocol of 2-[3-meth-oxy-4-(2-oxiranylmeth-oxy)phen-yl]-3-methyl-oxirane (GEEp-isoEu), a di-epoxy-dized monomer used in the manufacturing of thermosetting resins and intended for the elaboration of bio-composites.

Stepwise Oxidative C-C Coupling and/or C-N Fusion of Zn(II) meso-Pyridin-2-ylthio-porphyrins.

The synthesis and characterization of zinc(II) meso-pyridin-2-ylthio-porphyrins are presented in this manuscript. The (electro)chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(p-tolyl)-15-phenylporphyrinato] zinc(II) or [5,15-bis(pyridin-2-ylthio)-10,20-bis(p-tolyl)porphyrinato] zinc(II) leads to the formation of one or two C-N bond(s) by intramolecular nucleophilic attack of the peripheral thiopyridinyl fragment(s) on the neighboring ß-pyrrolic position(s) (C-N fusion reaction). In addition, the chemical oxidation of [5-(pyridin-2-ylthio)-10,20-bis(p-tolyl)porphyrinato] zinc(II), i.e., bearing one free meso position, mainly affords the meso,meso-dimer. Further stepwise electrochemical oxidation selectively produces the mono and bis C-N fused meso,meso-dimer. The resulting pyridinium derivatives exhibit important changes in their physicochemical properties (NMR, UV-vis, CV) as compared to their initial unfused precursors. Also, the X-ray crystallographic structures of three unfused monomers, one unfused meso,meso-dimer, and two C-N fused monomers are presented.

Template Synthesis of NPN' Pincer-type Ligands at Titanium Using an Ambiphilic Phosphide Scaffold.

Ti-imido complex [TiCl(NtBu)(BIPP)] [1; BIPP = bis(iminophosphoranyl)phosphide ligand] reacts with terminal alkynes R-C≡CH (R = phenyl, isopropenyl, cyclopropyl, and 2-pyridyl) via P-P bond cleavage of the BIPP ligand. The resulting complexes [TiCl(NPN')(NPhPPh2)] (2a-d) contain a pincer-type NPN' phosphide ligand that incorporates the terminal alkyne and the imido ligand from complex 1. Complexes 2a-d feature two chiral centers (Ti and P) with interdependent absolute configurations; thus, they are formed stereoselectively. Complex 2a (R = phenyl) undergoes chloride abstraction with [Et3SiHSiEt3][B(C6F5)4], yielding [Ti(NPN')(NPhPPh2)][B(C6F5)4] (3). Complex 3 is a moderately active and stereoselective initiator for the ring-opening polymerization of rac-lactide. Complex 3 activates the C═O bond of 4-iodobenzaldehyde to give complex 4 as a single diastereomer despite the presence of three chiral centers. Complex 3 undergoes transmetallation with SbCl3, yielding [Sb(NPN')][B(C6F5)4] (5) and [TiCl3(NPhPPh2)] (6) selectively. The bonding situation in 3 and 5 was analyzed using Bader's atoms in molecules and the electron localization function, showing that the nitrogen atoms of the NPN' ligand are electronically similar, and that the metal-phosphide interaction is more polar in the case of titanium.

Tetranuclear Dicationic Aurophilic Gold(I) Catalysts in Enyne Cycloisomerization: Cooperativity for a Dramatic Shift in Selectivity.

In comparison to mononuclear gold Lewis acid catalysts, digold complexes and dual-gold catalysis have illustrated a distinct and powerful potential for the activation of carbon-carbon multiple bonds. Herein, this concept is pushed further by designing novel tetranuclear gold(I) dicationic complexes structurally supported by strongly stabilizing constraint diphosphinoferrocenyl ligands and attractive closed-shell Au⋅⋅⋅Au aurophilic interactions. The use of a molecularly-defined tetranuclear dicationic aurophilic gold(I) precatalyst for the selectivity-challenging cycloisomerization of low-substituted 1,6-enynes favors the formation with high selectivity of strained azabicyclo[4.1.0]hept-4-enes - even in the complete absence of activating/orienting substituents on alkyne and olefin reactive functions. This selectivity is not achieved by the reported phosphine- and carbene-stabilized mono- and dinuclear cationic gold(I) complexes, including the ones formed from the same ligands. More importantly this selectivity differs also from nanoparticles and heterogeneous gold catalysts reported to date. DFT studies correlated to experimental mechanistic investigations support an unprecedented "cluster-like" reactivity from polynuclear cooperation at the origin of this peculiar selectivity where the aurophilic interactions preexist, and pre-organize, gold cluster reactive intermediates.

Gold modification by reduction of a diazonium salt prepared from an aliphatic diamine: a new useful means to remove hazardous substances.

We studied the electrochemical reduction based on gold electrode of a diazonium salt prepared from ethylenediamine. This is the first time where the covalent functionalization on the gold electrode of an alkyldiazonium salt, 2-aminoethane-1-diazonium chloride, is demonstrated. This step requires the preparation beforehand by diazotization of one amine group from ethylenediamine. The resulting electrodeposited ethylamine film was confirmed by spectroscopic characterizations from gold surface modification monitored by electrochemical quartz crystal microbalance (EQCM) coupled to cyclic voltammetry (CV). The development of chemosensors based on such a covalent functionalization of a metal can reduce the chemical threats to human health along with drastically removing contaminants according to the green chemistry principles.

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis.

Cationic amidotitanocene complexes [Cp2 Ti(NPhAr)][B(C6 F5 )4 ] (Cp=η5 -C5 H5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3 BNHMe2 results in fast homolytic Ti-N cleavage to give [Cp2 Ti(H3 BNHMe2 )][B(C6 F5 )4 ] (3). 1 a-c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H2 activation key step was disclosed using the Activation Strain Model (ASM).

Coordination Chemistry of a Bis(Tetrazine) Tweezer: A Case of Host-Guest Behavior with Silver Salts.

The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6-, BF4-, SbF6-, ClO4-, NTf2-, and OTf-. These compounds were characterized in the solid state by single-crystal X-ray diffraction (XRD) and diffuse reflectance spectroscopy, and in solution by 1H-NMR, mass spectrometry, electroanalysis, and UV-visible absorption spectrophotometry. The X-ray crystal structure of complexes {[Ag(3)][PF6]}∞ (4) and {[Ag(3)][SbF6]}∞ (6), where 3 is 3,3'-[(1,1'-biphenyl)-2,2'-diyl]-6,6'-bis(phenyl)-1,2,4,5-tetrazine, revealed the formation of 1D polymeric chains, characterized by an evolution to a large opening of the original tweezer and a coordination of silver(I) via two chelating nitrogen atom and some C=C π-interactions. Electrochemical and UV spectroscopic properties of the original tweezer and of the corresponding silver complexes are reported and compared. 1H-NMR titrations with AgNTf2 allowed the determination of the stoichiometry and apparent stability of two solution species, namely [Ag(3)]+ and [Ag(3)2]2+, that formed in CDCl3/CD3OD 2:1 v/v mixtures.

Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold-Catalyzed Enyne Cycloisomerization.

Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, iso-propyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear two-coordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-catalysed cycloisomerization. Cationic linear digold(I) bis(dicyclohexylphosphino) ferrocenes outperform other catalysts in the demanding regioselective cycloisomerization of enyne sulphonamides into cyclohexadienes. Conversely, tetrahedral and trigonal cationic monogold(I) complexes were found incompetent for enyne cycloaddition. We used the two-coordinate linear electron-rich Au(I) complex 2 b (R=Cy) to extend the scope of selective intramolecular cycloaddition of different 1,6-enyne sulfonylamines with high activity and excellent selectivity to the endo cyclohexadiene products.

Phosphasalen group IV metal complexes: synthesis, characterization and ring opening polymerization of lactide.

We report the synthesis of a series of Zr and Ti complexes bearing phosphasalen which differs from salen by the incorporation of two P atoms in the ligand backbone. The reaction of phosphasalen proligands (1a-1c)H2 with Zr(CH2Ph)4 led to different products depending on the nature of the N,N-linker in the ligand. In the case of ethylene-linked phosphasalen, octahedral Zr complex 2a formed as a single stereoisomer in trans geometry. With the phenylene linker, it was shown by dynamic NMR spectroscopy that complex 2b exists as a mixture of trans and cis-ß isomers in solution, both enantiomers (Δ and Λ) of the cis-ß isomer being in fast equilibrium with respect to the NMR time-scale. The use of a propylene-linked phosphasalen proligand 1cH2 led to a mixture of complexes among which a binuclear Zr complex 2c bridged only by one phosphasalen ligand could be isolated and characterized. Addition of 2 equiv. of iPrOH to 2a and 2b afforded diisoproxy Zr complexes 3a and 3b as a mixture of trans and cis-ß isomers, the latter undergoing fast Δ/Λ isomerization in solution. Addition of B(C6F5)3 to 2a and 2b gave cationic monobenzyl Zr complexes 4a and 4b which have been further converted into cationic alkoxy Zr complexes 5a-b and 6a-b by alcoholysis with iPrOH and (S)-methyl-lactate, respectively. The reaction of the phosphasalen proligands with Ti(NMe2)4 proceeded diastereoselectively giving rise to Ti complexes 7a-c in octahedral geometry with cis-ß wrapping of the ligand. The complexes have been tested for the ROP of rac-lactide. The neutral phosphasalen Ti and Zr complexes showed only poor activity probably due to the encumbered and electron donating nature of the phosphasalen ligand. In contrast, the cationic Zr alkoxides 5a, 6a and 6b are effective initiators for the controlled and hetero-selective ROP of rac-lactide.

Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis.

The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the central phosphorus atom enables the formation of d0-d10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus-metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu-Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P-P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium (TP) cations; (ii) the P-P bonds are normal covalent (i.e. not dative) in both BIPP and TP.

Bridge-Clamp Bis(tetrazine)s with [N]8 π-Stacking Interactions and Azido-s-Aryl Tetrazines: Two Classes of Doubly Clickable Tetrazines.

Click chemistry at a tetrazine core is useful for bioorthogonal labeling and crosslinking. Introduced here are two new classes of doubly clickable s-aryl tetrazines synthesized by Cu-catalyzed cross-coupling. Homocoupling of o-brominated s-aryl tetrazines leads to bis(tetrazine)s structurally characterized by tetrazine cores arranged face-to-face. [N]8 π-stacking interactions are essential to the conformation. Upon inverse electron demand Diels-Alder (iEDDA) cycloaddition, the bis(tetrazine)s produce a unique staple structure. The o-azidation of s-aryl tetrazines introduces a second proximal intermolecular clickable function that leads to double click chemistry opportunities. The stepwise introduction of fluorophores and then iEDDA cycloaddition, including bioconjugation to antibodies, was achieved on this class of tetrazines. This method extends to (thio)etherification, phosphination, trifluoromethylation and the introduction of various bioactive nitrogen-based heterocycles.

Regioselective C-H amination of free base porphyrins via electrogenerated pyridinium-porphyrins and stabilization of easily oxidized amino-porphyrins by protonation.

Four free base aminoporphyrins were synthesized in two steps via regioselective anodic nucleophilic substitution with pyridine followed by ring opening of the electrogenerated pyridinium with piperidine. The X-ray crystallographic structure of the unstable 2-aminotetraphenylporphyrin was solved. Protonation of this latter compound leads to the stable diiminium porphyrin salt.

A sterically congested 1,2-diphosphino-1'-boryl-ferrocene: synthesis, characterization and coordination to platinum.

A new class of tritopic ferrocene-based ambiphilic compounds has been prepared by assembling diphosphino- and boryl-substituted cyclopentadienides at iron. The presence of five sterically demanding substituents on the ferrocene platform induces conformational constraints, as is apparent from XRD and NMR data, but does not prevent the chelating coordination to platinum. The Lewis acid moiety is pendant in both the free ligand and the platinum complex.

Oxidative C-N fusion of pyridinyl-substituted porphyrins.

The mild (electro)chemical oxidation of pyridin-2-ylthio-meso substituted Ni(ii) porphyrins affords C-N fused cationic and dicationic pyridinium-based derivatives. These porphyrins are fully characterized and the molecular structure of one of them was confirmed by X-ray crystallography. A mechanism for the intramolecular oxidative C-N coupling is proposed based on theoretical calculations and cyclic voltammetry analyses.