Hydrogen Bonding in Platinum Indolylphosphine Polyfluorido and Fluorido Complexes.

The reaction of the Pt complexes cis-[Pt(CH3 )(Ar){Ph2 P(Ind)}2 ] (Ind=2-(3-methyl)indolyl, Ar=4-tBuC6 H4 (1 a), 4-CH3 C6 H4 (1 b), Ph (1 c), 4-FC6 H4 (1 d), 4-ClC6 H4 (1 e), 4-CF3 C6 H4 (1 f)) with HF afforded the polyfluorido complexes trans-[Pt(F(HF)2 )(Ar){Ph2 P(Ind)}2 ] 2 a-f, which can be converted into the fluoride derivatives trans-[Pt(F)(Ar){Ph2 P(Ind)}2 ] (3 a-f) by treatment with CsF. The compounds 2 a-f and 3 a-f were characterised thoroughly by multinuclear NMR spectroscopy. The data reveal hydrogen bonding of the fluorido ligand with HF molecules and the indolylphosphine ligand. Polyfluorido complexes 2 a-f show larger |1 J(F,Pt)|, but lower 1 J(H,F) coupling constants when compared to the fluorido complexes 3 a-f. Decreasing 1 J(P,Pt) coupling constants in 2 a-f and 3 a-f suggest a cis influence of the aryl ligands in the following order: 4-tBuC6 H4 (a) ≈4-CH3 C6 H4 (b)

Reactivity of Xantphos-Type Rhodium Complexes Towards SF4 : SF3 Versus SF2 Complex Generation.

S-F-bond activation of sulfur tetrafluoride at [Rh(Cl)(tBu xanPOP)] (1; tBu xanPOP=9,9-dimethyl-4,5-bis-(di-tert-butylphosphino)-xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF2 )(tBu xanPOP)][SF5 ] (2 a) together with trans-[Rh(Cl)(F)2 (tBu xanPOP)] (3) and cis-[Rh(Cl)2 (F)(tBu xanPOP)] (4) which both could also be obtained by the reaction of SF5 Cl with 1. In contrast to that, the conversion of SF4 at the methyl complex [Rh(Me)(tBu xanPOP)] (5) gave the isolable and room-temperature stable cationic λ4 -trifluorosulfanyl complex [Rh(Me)(SF3 )(tBu xanPOP)][SF5 ] (6). Treatment of 6 with the Lewis acids BF3 or AsF5 produced the dicationic difluorosulfanyl complex [Rh(Me)(SF2 )(tBu xanPOP)][BF4 ]2 (8 a) or [Rh(Me)(SF2 )(tBu xanPOP)][AsF6 ]2 (8 b), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF3 )(tBu xanPOP)][BF4 ] (9). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF2 )(tBu xanPOP)][Cl] (2 b) together with chloromethane and SF5 Cl.

Platinum-Catalyzed Hydrofluorination of Alkynes: Hydrogen Bonding to Indolylphosphine Ligands to Provide Fluoride Reactivity.

The reaction of the Pt complexes cis-[Pt(CH3 )2 {R2 P(Ind)}2 ] (Ind=2-(3-methyl)indolyl, R=Ph (1 a), 4-FC6 H4 (1 b), 4-CF3 C6 H4 (1 c)) with HF afforded the fluorido complexes trans-[Pt(F(HF)2 )(CH3 ){R2 P(Ind)}2 ] 2 a-c, which can be converted into trans-[Pt(F)(CH3 ){R2 P(Ind)}2 ] (3 a-c) by treatment with CsF. Addition of 3-hexyne to 2 a-c gave alkyne complexes trans-[Pt(C,C-η2 -C2 H5 C≡CC2 H5 )(CH3 ){R2 P(Ind)}2 {F(HF)2 }] (4 a-c) at which a fluoride is stabilised as polyfluoride in the coordination sphere by hydrogen bonding to the indolyl-substituted phosphine ligands. Subsequent heating of a solution of 4 a in the presence of PVPHF led to fluoroalkene formation. Selective catalytic hydrofluorination of alkynes to yield (Z)-fluoroalkenes were developed. The ability of hydrogen bonding to polyfluoride favours the fluorination step as demonstrated by studies with complexes bearing no indolyl groups at the phosphine ligands.

Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation, Fluoride Migration, and Hydrogen Bonding.

The reaction of [PtCl2 (COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr2 P(C9 H8 N)) led to the formation of the platinum(ii) chlorido complexes, cis-[PtCl2 {iPr2 P(C9 H8 N)}2 ] (1) and trans-[PtCl2 {iPr2 P(C9 H8 N)}2 ] (2). The cis-complex 1 reacted with NEt3 yielding the complex cis-[PtCl{κ2 -(P,N)-iPr2 P(C9 H7 N)}{iPr2 P(C9 H8 N)}] (3) bearing a cyclometalated κ2 -(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt3 . Treatment of 1 or 3 with (CH3 )4 NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ2 -(P,N)-iPr2 P(C9 H7 N)}2 ] (4). The molecular structures of the complexes 1-4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ2 -(P,N)-iPr2 P(C9 H7 N)}{iPr2 P(C9 H8 N)}] ⋅ (HF)4 (5 ⋅ (HF)4 ) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii) fluorido complex 5 ⋅ (HF)4 exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3, complex 5 ⋅ (HF)4 reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ2 -(P,C)-iPr2 P(C9 H7 NCO)}{iPr2 P(C9 H8 N)}][F(HF)4 ] (7) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C3 H6 )}{κ2 -(P,N)-iPr2 P(C9 H7 N)}{iPr2 P(C9 H8 N)}][F(HF)4 ] (9), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9.

Characterisation of Elastomers as Food Contact Materials-Part 1: Quantification of Extractable Compounds, Swelling of Elastomers in Food Simulants and Release of Elements.

Elastomers are not a uniform class of materials but comprise a broad spectrum of chemically different polymers. Sealing gaskets, gloves, teats, conveyor belts and tubing are examples of elastomers being used as food contact materials (FCMs). Ten elastomer samples were evaluated with respect to the content of extractable compounds, migration of substances into ethanolic food simulants, swelling in food simulants and release of elements in different food simulants. The number of extractable substances <1000 Da was determined by comprehensive two-dimensional gas chromatography coupled with flame ionisation detection (GC × GC-FID) analysis of tetrahydrofuran (THF) extracts. The number of signals ranged from 61 (a thermoplastic elastomer (TPE)) to 690 (a natural rubber/styrene-butadiene-rubber blend (NR/SBR)). As for risk assessment, the decisive factor is which substances reach the food. The extent of substances that migrate into ethanolic food simulants was investigated. Elastomer FCMs can be the source of food contamination with heavy metals. Notably, contamination with lead was detected in some samples investigated in this study. It was shown that food simulants harbour the potential to morphologically alter or even disintegrate elastomeric materials. The results presented here highlight the importance to carefully choose the elastomer type for the intended use as FCMs as not every application may prove safe for consumers.

Release of Melamine and Formaldehyde from Melamine-Formaldehyde Plastic Kitchenware.

The release of melamine and formaldehyde from kitchenware made of melamine resins is still a matter of great concern. To investigate the migration and release behavior of the monomers from melamine-based food contact materials into food simulants and food stuffs, cooking spoons were tested under so-called hot plate conditions at 100 °C. Release conditions using the real hot plate conditions with 3% acetic acid were compared with conditions in a conventional migration oven and with a release to deionized water. Furthermore, the kinetics of the release were studied using Arrhenius plots giving an activation energy for the release of melamine of 120 kJ/mol. Finally, a correlation between quality of the resins, specifically the kind of bridges between the monomers, and the release of melamine, was confirmed by CP/MAS 13C-NMR measurements of the melamine kitchenware. Obviously, the ratio of methylene bridges and dimethylene ether bridges connecting the melamine monomers during the curing process can be directly correlated with the amount of the monomers released into food.

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

The rhodium(i) complexes [Rh(Bpin)(PEt3)3] (1), [Rh(H)(PEt3)3] (5) and [Rh(Me)(PEt3)3] (14) were employed in reactions with pentafluorostyrene affording coordination of the olefin and C-F or C-H bond activation. Control of the reaction conditions allowed for selective activation reactions at different positions at the fluorinated aromatic ring. The rhodacycle trans-[Rh(F)(CH2CH2(2-C6F4))(PEt3)2] (7) was identified as an intermediate for an activation at the 2-position. Reactivity studies of the latter with CO led to the generation of trans-[Rh(F)(CH2CH2C6F4)(CO)(PEt3)2] (10). Stoichiometric and catalytic hydroboration reactions were achieved using complexes 1 or 5 as catalysts.

Release of aluminium and thallium ions from uncoated food contact materials made of aluminium alloys into food and food simulant.

In order to investigate the release of aluminium ions from food contact materials, three different types of uncoated aluminium menu trays for single use were tested with the foodstuffs sauerkraut juice, apple sauce and tomato puree, as well as with the food simulants 5 g/L citric acid solution and artificial tap water. To mimic a consumer relevant exposure scenario, the aluminium trays were studied using time and temperature gradients according to the Cook & Chill method, also taking into account storage time at elevated temperatures during the delivery period. The release of aluminium was found to exceed the specific release limit (SRL) of 5 mg aluminium per kilogram of food specified by the Council of Europe by up to six times. Furthermore, a release of thallium was also detected unexpectedly. Kinetic studies showed a comparable behaviour in the release of aluminium, manganese and vanadium as components of the aluminium alloy itself. In contrast, thallium could be identified as a surface contaminant or impurity because of an entirely different kinetic curve. Kinetic studies also allowed activation energy calculations. Additional camping saucepans were tested as an article for repeated use. In three subsequent release experiments with citric acid (5 g/L), artificial tap water and tomato puree as benchmark foodstuffs, the results were comparable to those of the uncoated wrought alloy aluminium trays.

Transfer of primary aromatic amines from coloured paper napkins into four different food matrices and into cold water extracts.

The aim of this study was to compare the transfer of primary aromatic amines (PAAs) from napkins into cold water extract (CWE) with transfer into four different food matrices. An HPLC-MS/MS multi-analyte method for quantification of 26 PAAs in CWE was validated and applied. In addition, the method was validated for seven different PAAs in four different food matrices (cucumber, rice, pickled gherkin and butter cookie) representing wet, dry, acidic and fatty food. The CWEs of 12 coloured napkin samples were analysed, and 3 napkins released more than 0.01 mg kg-1 PAAs into the CWE. These three napkins were chosen for transfer testing with food samples. In total, seven different PAAs were quantified in the food samples. Results show that the transfer of the tested PAAs into the CWE is in most cases comparable to the transfer into the tested food samples. In some cases, the CWE overestimates transfer into food, except for the transfer of aniline into pickled gherkin, where the CWE underestimates transfer. Therefore, the CWE serves as an adequate and certainly not overestimating simulation of reality for the tested transfer of PAAs into the food samples.

Synthesis and structure of rhodium(i) silyl carbonyl complexes: photochemical C-F and C-H bond activation of fluorinated aromatic compounds.

The rhodium(i) silyl carbonyl complexes [Rh{Si(OEt)3}(CO)(dippp)] () and [Rh{Si(OEt)3}(CO)(dippe)] () (dippp = 1,3-bis(diisopropylphosphino)propane, dippe = 1,2-bis-(diisopropylphosphino)ethane) were synthesized on treatment of the methyl compounds [Rh(CH3)(CO)(dippp)] () or [Rh(CH3)(CO)(dippe)] () with HSi(OEt)3 at low temperature. The methyl complexes and were prepared starting from the binuclear complexes [{Rh(µ-Cl)(dippp)}2] () and [{Rh(µ-Cl)(dippe)}2] (), respectively. The silyl complexes and as well as the precursors [{Rh(µ-I)(dippp)}2] (), [Rh(X)(CO)(dippp)] (: X = CH3, : X = I) and [Rh(X)(CO)(dippe)] (: X = CH3, : X = Cl) were characterized by NMR and IR spectroscopy and the structures in the solid state were determined by X-ray crystallography. The silyl complex converts into the carbonyl-bridged complex [{Rh(µ-CO)(dippp)}2] () above temperatures of -30 °C by loss of the silyl ligand, whereas is more thermally stable and a reaction to the binuclear complex [{Rh(µ-CO)(dippe)}2] () was observed at 50 °C. The silyl complex reacted under irradiation with hexafluorobenzene and pentafluoropyridine to give the C-F activation products [Rh(C6F5)(CO)(dippe)] () and [Rh(2-C5F4N)(CO)(dippe)] (), respectively. As additional products the silyl dicarbonyl complex [Rh{Si(OEt)3}(CO)2(dippe)] () and the cationic complex [Rh2(µ-H)(µ-CO)2(dippe)2](+)[SiF5](-) () were identified. Compound was synthesized independently by treatment of with gaseous CO. In a similar manner, the dippp analogue [Rh{Si(OEt)3}(CO)2(dippp)] () was also prepared starting from . Photochemical reaction of with pentafluorobenzene and 2,3,5,6-tetrafluoropyridine resulted selectively in C-H bond activation to afford and [Rh(4-C5F4N)(CO)(dippe)] (), respectively.