New Fluorine-Containing Diamine Monomers for Potentially Improved Polyimides.

Two new fluorine-containing diamine monomers were designed with the goal of reducing charge transfer complex (CTC) interactions between neighboring chains in polyimides (i.e., high transparency/low color) while hopefully maintaining the well-known thermal stability and flexibility generally associated with polyimides. The proposed diamines have been prepared through (1) the functionalization of 1,3-bis[(pentafluorobenzyl)oxy]benzene with 4-aminophenol and (2) the addition of 2-chloro-5-nitrobenzotrifluoride to 4,4'-bicyclohexanol followed by reduction of the resulting dinitro compound. The new compounds have been characterized by multinuclear NMR and IR spectroscopy and high-resolution liquid chromatography-mass spectrometry as well as single-crystal X-ray diffraction on the new diamine prepared from 4,4'-bicyclohexanol. Not only was the structure of the proposed new diamine confirmed, but another interesting example of hydrogen bonding between an N-H proton and the π-system of an aromatic ring was observed and documented. Initial polymerizations have been carried out via the two-step imidization process.

A New Motif in Halogen Bonding: Cooperative Intermolecular S-Br⋠⋠⋠O, O⋠⋠⋠F, and F⋠⋠⋠F Associations in the Crystal Packing of α,ω-Di(sulfonyl bromide) Perfluoroalkanes.

We recently reported the first examples of S-Cl⋅⋅⋅O halogen bonding complemented by short F⋅⋅⋅F contacts between neighboring chains that resulted in stabilized crystals of ClSO2 (CF2 )4 SO2 Cl and ClSO2 (CF2 )6 SO2 Cl. More recently, other researchers studied our crystallographic data further using an Independent Gradient Model (IGM), and they suggested if one goes beyond IUPAC's proposed 'less than the sum of the van der Waals radii' criterion that even more noncovalent interactions between fluorine atoms on neighboring chains as well as Cl⋅⋅⋅Cl, Cl⋅⋅⋅S, O⋅⋅⋅F, and O⋅⋅⋅S attractive interactions can be found. With that said, we have prepared samples of the related BrSO2 (CF2 )n SO2 Br derivatives (where n=4, 6, 8, and others), which give rise to even stronger S-Br⋅⋅⋅O halogen bonding interactions complemented minimally by O⋅⋅⋅F and F⋅⋅⋅F intermolecular interactions as shown by X-ray crystallography and computational chemistry using IGM isosurface plots. Additional spectroscopic characterization (multinuclear NMR, FT-IR, and MS) of the disulfonyl bromide derivatives BrSO2 (CF2 )4 SO2 Br, BrSO2 (CF2 )6 SO2 Br, and BrSO2 (CF2 )8 SO2 Br has also been obtained as well as some preliminary spectroscopic evidence for BrSO2 (CF2 )2 SO2 Br and BrSO2 CF2 O(CF2 )2 OCF2 SO2 Br. The implication of these results toward the preparation of the corresponding disulfonyl iodides is discussed.

Synthesis and [3,3]-sigmatropic rearrangements of 5-(pentafluorosulfanyl)-pent-3-en-2-ol, its homologues, and trifluoromethyl analogues.

The synthesis of aliphatic (pentafluoro-λ6-sulfanyl)(SF5)-substituted compounds is more challenging than that of the related CF3-substituted analogues. Previous investigations of [3,3]-sigmatropic rearrangements of γ-SF5-substituted allylic alcohols failed to yield 3-SF5-substituted carboxylic acid derivatives. Herein, we present the synthesis of a series of 1-SF5-alk-1-en-3-ols and our efforts to apply them in Johnson-Claisen, ester enolate-Claisen, and Ireland-Claisen rearrangements. Unfortunately, these reactions failed to include the 1-SF5-substituted 1,2-double bond, although successful reactions of analogous CF3-allylic alcohols were reported. Further experiments revealed that bulkiness rather than electronic properties of the SF5 group prevented [3,3]-sigmatropic rearrangements. Indeed, the introduction of a competing second vinyl group into the system (1-SF5-penta-1,4-dien-3-ol) confirmed that a Johnson-Claisen rearrangement was successful (92% yield of methyl 7-SF5-hepta-4,6-dienoate) with incorporation of the unsubstituted 4,5-double bond while the 1-SF5-substituted 1,2-double bond remained unchanged. Efforts to apply 1-(SF5CF2)-substituted 1,2-double bond systems, which are similar to CF3 analogues in steric requirements, in Johnson-Claisen or ester enolate-Claisen rearrangements failed because of the instability of the SF5CF2 substituent under various reaction conditions. On the other hand, when the SF5 group was separated from the reaction center by a CH2 group instead (5-SF5-pent-3-en-2-ol), Johnson-Claisen rearrangements using six orthoesters provided the target 2-substituted 3-(CH2SF5)-hex-4-enoates in 55-76% yields as ∼1 : 1 mixtures of diastereomers. As an example to demonstrate the utility of these products, methyl 3-(CH2SF5)-hex-4-enoate was reduced, and the formed alcohol was oxidized to the aldehyde. Finally, initial experiments showed that the synthetic sequence developed for SF5 compounds is also applicable for analogous CF3-substituted allylic alcohols (5-CF3-pent-3-en-2-ol) and their Johnson-Claisen rearrangement.

Neutron Diffraction Study of Significant sp3 and sp2 C-H Bond Shortening in a Fluorinated Pyridinium Saccharinate.

We have experimentally shown by neutron diffraction significant shortening of both sp3- and sp2-hybridized C-H bonds to 1.092(2) and 1.081(1) Å in a hydrogen-bonded crystal of a difluorinated compound, 4-((2,2-difluoroethoxy)methyl)pyridinium saccharinate. Both MP2 and DFT calculations affirmed the C-H bond shrinkages. Sanderson's electronegativity equalization principle provides insight into the shortening of the C-H covalent bond lengths for both sp3- and sp2-hybridized carbon atoms. To the best of our knowledge, this neutron diffraction study has revealed the largest extents of sp3 and sp2 C-H bond shrinkages with a 3-sigma rule being satisfied.

Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ6-sulfanyl)acetic acid esters with aldehydes.

Aldol reactions belong to the most frequently used C-C bond forming transformations utilized particularly for the construction of complex structures. The selectivity of these reactions depends on the geometry of the intermediate enolates. Here, we have reacted octyl pentafluoro-λ6-sulfanylacetate with substituted benzaldehydes and acetaldehyde under the conditions of the silicon-mediated Mukaiyama aldol reaction. The transformations proceeded with high diastereoselectivity. In case of benzaldehydes with electron-withdrawing substituents in the para-position, syn-α-SF5-ß-hydroxyalkanoic acid esters were produced. The reaction was also successful with meta-substituted benzaldehydes and o-fluorobenzaldehyde. In contrast, p-methyl-, p-methoxy-, and p-ethoxybenzaldehydes led selectively to aldol condensation products with (E)-configured double bonds in 30-40% yields. In preliminary experiments with an SF5-substituted acetic acid morpholide and p-nitrobenzaldehyde, a low amount of an aldol product was formed under similar conditions.

Side-chain conformations in the isomorphous polyfluorinated {4,4'-bis[(2,2-difluoroethoxy)methyl]-2,2'-bipyridine-κ2N,N'}dichloridopalladium and -platinum complexes.

The polyfluorinated title compounds, [MCl2(C16H16F4N2O2)] or [4,4'-(HCF2CH2OCH2)2-2,2'-bpy]MCl2 [M = Pd, (1), and M = Pt, (2)], have -C(Hα)2OC(Hß)2CF2H side chains with H-atom donors at the α and ß sites. The structures of (1) and (2) are isomorphous, with the nearly planar (bpy)MCl2 molecules stacked in columns. Within one column, π-dimer pairs alternate between a π-dimer pair reinforced with C-H...Cl hydrogen bonds (α,α) and a π-dimer pair reinforced with C-Hß...F(-C) interactions (abbreviated as C-Hß...F-C,C-Hß...F-C). The compounds [4,4'-(CF3CH2OCH2)2-2,2'-bpy]MCl2 [M = Pd, (3), and M = Pt, (4)] have been reported to be isomorphous [Lu et al. (2012). J. Fluorine Chem. 137, 54-56], yet with disorder in the fluorous regions. The molecules of (3) [or (4)] also form similar stacks, but with alternating π-dimer pairs between the (α,ß; α,ß) and (ß,ß) forms. Through (C-)H...Cl hydrogen-bond interactions, one molecule of (1) [or (2)] is expanded into an aggregate of two inversion-related π-dimer pairs, one pair in the (α,α) form and the other pair in the (C-Hß...F-C,C-Hß...F-C) form, with the plane normals making an interplanar angle of 58.24 (3)°. Due to the demands of maintaining a high coordination number around the metal-bound Cl atoms in molecule (1) [or (2)], the ponytails of molecule (1) [or (2)] bend outward; in contrast, the ponytails of molecule (3) [or (4)] bend inward.

Weak hydrogen and halogen bonding in 4-[(2,2-difluoroethoxy)methyl]pyridinium iodide and 4-[(3-chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide.

To enable a comparison between a C-H...X hydrogen bond and a halogen bond, the structures of two fluorous-substituted pyridinium iodide salts have been determined. 4-[(2,2-Difluoroethoxy)methyl]pyridinium iodide, C8H10F2NO+·I-, (1), has a -CH2OCH2CF2H substituent at the para position of the pyridinium ring and 4-[(3-chloro-2,2,3,3-tetrafluoropropoxy)methyl]pyridinium iodide, C9H9ClF4NO+·I-, (2), has a -CH2OCH2CF2CF2Cl substituent at the para position of the pyridinium ring. In salt (1), the iodide anion is involved in one N-H...I and three C-H...I hydrogen bonds, which, together with C-H...F hydrogen bonds, link the cations and anions into a three-dimensional network. For salt (2), the iodide anion is involved in one N-H...I hydrogen bond, two C-H...I hydrogen bonds and one C-Cl...I halogen bond; additional C-H...F and C-F...F interactions link the cations and anions into a three-dimensional arrangement.

Synthesis of α-(Pentafluorosulfanyl)- and α-(Trifluoromethyl)-Substituted Carboxylic Acid Derivatives by Ireland-Claisen Rearrangement.

Earlier studies have shown that [3,3]-sigmatropic rearrangements of allyl esters are useful for the construction of fluorine-containing carboxylic acid derivatives. This paper describes the synthesis of 3-aryl-pent-4-enoic acid derivatives bearing either a pentafluorosulfanyl (SF5) or a trifluoromethyl (CF3) substituent in the 2-position by treatment of corresponding SF5- or CF3-acetates of p-substituted cinnamyl alcohols with triethylamine followed by trimethylsilyl triflate (TMSOTf). This Ireland-Claisen rearrangement delivered approximate 1:1 mixtures of syn/anti diastereoisomers due to tiny differences (<0.5 kcal/mol) both in the energy of (Z)/(E)-isomeric ester enolates and in the alternative Zimmerman-Traxler transition states of model compounds as shown by DFT calculations. Acidic reaction conditions have to be avoided since addition of the reagents in opposite sequence (first TMSOTf then Et3N) led to oligomerization of the cinnamyl SF5- and CF3-acetates. Treatment of the corresponding regioisomeric 1-phenyl-prop-2-en-1-yl acetates under the latter conditions resulted in [1,3]-sigmatropic rearrangement and subsequent oligomerization of the intermediately formed cinnamyl esters. When Et3N was added first followed by TMSOTf, no further reaction of the formed ester was detected.

Synthesis of SF5CF2-Containing Enones and Instability of This Group in Specific Chemical Environments and Reaction Conditions.

The chemistry of the SF5CF2 moiety has been scarcely investigated. In this report, we present synthetic pathways to a variety of SF5CF2-substituted compounds starting from vinyl ethers and SF5CF2C(O)Cl. In specific chemical environments and under particular reaction conditions, the SF5CF2 moiety is unstable in downstream products resulting in the elimination of the SF5(-) anion and its decomposition to SF4 and F(-). Surprisingly, the formed F(-) can attack the intermediate difluorovinyl moiety to form trifluoromethyl substituted products. This appears to happen when an intermediate neighboring group participation involving a double bond is possible. Under slightly different conditions, the reaction stops at the stage of a difluorovinyl compound.

Anti-Selective Aldol Reactions of Pentafluorosulfanylacetic Acid Esters with Aldehydes Mediated by Dicyclohexylchloroborane.

Aldol reactions of pentafluorosulfanyl (SF5)-substituted acetic acid esters with both aromatic and aliphatic aldehydes proceeded with excellent anti-diastereoselectivity and good to high yields using dicyclohexylchloroborane/triethylamine. This methodology enabled the synthesis of hitherto unknown α-SF5-ß-hydroxy esters. Using a norephedrine-based auxiliary, high asymmetric induction was observed. The stereochemistry of products was assigned by NMR spectroscopy and proved by X-ray diffraction analysis. The intermediate enolate was identified as a highly unstable species.

Ambiphilic properties of SF5CF2CF2Br derived perfluorinated radical in addition reactions across carbon-carbon double bonds.

The extraordinary properties of the pentafluorosulfanyl (SF5) group attract attention of organic chemists. While numerous SF5-substituted compounds have been synthesized, the direct introduction of SF5(CF2)n moieties has remained almost unexplored. Our investigations revealed the ambiphilic character of the SF5CF2CF2 radical. Addition reactions to electron-rich or electron-deficient alkenes profit either from its electrophilic or nucleophilic properties. Thus, the readily available SF5CF2CF2Br proved to be a promising and versatile building block for the introduction of this perfluorinated moiety.

Pentafluorosulfanyldifluoroacetic acid: rebirth of a promising building block.

Three novel, easily scalable routes for the synthesis of pentafluorosulfanyldifluoroacetic acid, SF5CF2C(O)OH, are described. Reactions of its acid chloride with amines and alcohols led to a small library of 15 amides and five esters, respectively. The reaction of the acid chloride with phenylmagnesium bromide gave the corresponding acetophenone. Pentafluorosulfanyldifluoroacetonitrile was obtained from pentafluorosulfanyldifluoroacetamide by dehydration with diphosphorus pentoxide.

Synthesis and electrocatalytic activity of photoreduced platinum nanoparticles in a poly(ethylenimine) matrix.

Monodisperse polymer-mediated platinum (Pt) nanoparticles (NPs) have been synthesized by photoreduction in the presence of poly(ethylenimine) (PEI), a hyperbranched polymer. The formation process of the Pt NPs is pursued by UV-vis spectroscopy, and the formation mechanism is discussed. The morphology and size of the Pt NPs were characterized by transmission electron microscopy (TEM). TEM imaging shows that the Pt NPs' average diameter is 2.88 +/- 0.53 nm. The PEI/Pt NPs were immobilized on glassy carbon electrodes, and the electrocatalytic activity of the catalysts was investigated by cyclic voltammetry. PEI/Pt NPs exhibit very high catalytic activity for a methanol oxidation reaction. PEI/Pt NPs on glassy carbon electrodes are robust, showing good tolerance to poisoning even after many cycles. The electrocatalytic activity of PEI/Pt NPs compares favorably with other polymer-mediated Pt NPs. The results indicate that PEI is an appropriate complexing reducing agent for the photochemical production of Pt NPs and a good capping agent, allowing immobilization of the NPs on the working electrode.

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs (including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.

Pentafluoronitrosulfane, SF5NO2.

The synthesis of pentafluoronitrosulfane, SF5NO2, is accomplished either by reacting N(SF5)3 with NO2 or by the photolysis of a SF5Br/NO2 mixture using diazo lamps. The product is purified by treatment with CsF and repeated trap-to-trap condensation. The solid compound melts at -78 degrees C, and the extrapolated boiling point is 9 degrees C. SF5NO2 is characterized by 19F, 15N NMR, IR, Raman, and UV spectroscopy as well as by mass spectrometry. The molecular structure of SF5NO2 is determined by gas electron diffraction. The molecule possesses C2v symmetry with the NO2 group staggering the equatorial S-F bonds and an extremely long 1.903(7) Angstroms S-N bond. Calculated bond enthalpies depend strongly on the computational method: 159 (MP2/6-311G++(3df)) and 87 kJ mol(-1) (B3LYP/6-311++G(3df)). The experimental geometry and vibrational spectrum are reproduced reasonably well by quantum chemical calculations.