Zinc hexafluorophosphate

Gable, R. W., Hoskins, B. F., and Robson, R., A new type of interpenetration involving enmeshed independent square grid sheets. The structure of diaquabis-(4,4 -bipyridine)zinc hexafluorophosphate, Chem. Commun., 1677-1678 (1990). 

In a very recent study, it has been demonstrated116 that zinc 5,15-bis(3,5-di-tert-butylphenyl)-porphyrin (13) without any activating halogen atoms at the chromophore can be directly linked in a very simple oxidative coupling reaction with silver(I) hexafluorophosphate to a mixture of porphyrin dimers, trimers and tetramers. The separation of the product mixture was achieved by gel-permeation chromatography based on the molecular weights of the oligomers. The dimer when re-exposed to the same reaction conditions yielded 25% of the tetramer.116... 

As mentioned above, the conventional diazonium salts have good optical properties as CEL dyes and negative working sensitizers for the two-layer resist system. However, almost all diazonium salts are stabilized with metal-containing compounds such as zinc chloride, tetrafluoroborate, hexafluoro-antimonate, hexafluoroarsenate, or hexafluorophosphate, which may not be desirable in semiconductor fabrication because of potential device contamination. To alleviate the potential problem, new metal-free materials have been sought for. 

This structural change is suppressed by the addition of tetrahydrothiophene (THT)19b. It prevents the formation of polymethylene zinc, i.e. (—CH2Zn—) . Without THT, a solution of 3 in THF yields polymethylene zinc at 60 °C. Monomeric bis(iodozincio)methane (3) is much more active for methylenation as compared to polymethylene zinc. As shown in Table 3 (entry 3), the addition of THT to the reaction mixture at 60 °C improved the yield of the alkene dramatically. Practically, however, its stinking property makes the experimental procedure in large scale uncomfortable. Fortunately, an ionic Uquid, l-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), plays the same role. Ionic liquid also stabilizes the monomeric structure of 3 even at 60 °C and maintains it during the reaction at the same temperature. The method can be applied to various ketones as shown in Scheme 14.4... 

CIFgN4PZnC24H2g, Zinc(II), chloro(2,9-di-methyl-3,10-diphenyl-l, 4,8,11-tetraaza-cyclotetradeca-1,3,8,10-tetraene)-, hexafluorophosphate(l -), 22 111 CIFgTlCi2H2, Thallium(III), chlorobis-(2,3,4,6-tetrafluorophenyI-), 21 73 CIF9OC4, Hypochlorous acid, perfluoro-tert-butyl ester, 24 61... 

The ureidopyrimidone motif is hydrogen bonded in chloroform. On addition of FeCU and (CH3COO)2Zn, iro-n(II) complexes, and zinc(II) complexes are obtained, respectively, with both of them soluble in chloroform. On addition of ammonium hexafluorophosphate (counterion exchange), the polymer is precipitated. The polymer is film-forming and is transparent at lower film thickness. 

CH3HL2 (0.250 g, 0.5 mmol) was dissolved in methanol (20 mL), and a methanol solution (10 mL) of zinc(ll) acetate dihydrate (0.240 g, 0.9 mmol) was added dropwise. The resulting pale yellow solution was then heated under reflux for 0.5 h. The solution was permitted to cool to room temperature and sodium hexafluorophosphate (0.140 g, 0.8 mmol) was added. Upon standing colorless crystals were deposited and these were collected by filtration (0.31 g, 71 %). 

CH3HL3 (50 mg, 0.085 mmol) was dissolved in methanol (2 mL) and zinc(ll) acetate dihydrate (0.37 mg, 0.17 mmol) in methanol (3 mL) was added dropwise at room temperature. The pale yellow solution was refluxed for 30 min, cooled slowly to room temperature and subsequently sodium hexafluorophosphate (43 mg, 0.26 mmol) was added. Colorless crystals emerged upon standing after 2 h which were filtered and dried in air (49 %, 41 mg). 

BrHL2 (60 mg, 0.1 mmol) was dissolved in methanol (6 mL) and was combined with zinc(n) acetate dihydrate (49 mg, 0.2 mmol). The complex solution was subsequently refluxed for 30 min, cooled to room temperature and sodium hexa-fluorophosphate (57 mg, 0.3 mmol) was added. After filtration the solution was left in a beaker to evaporate at room temperature. Colorless crystals were obtained after 2 days which were suitable for X-ray crystallography (40 mg, 22 %). As the sodium hexafluorophosphate employed was wet, the complex crystallized with P03p instead of acetates as suggested by mass spectrometry, infrared spectroscopy and microanalysis. 

CH3HL4 (80 mg, 0.2 mmol) and zinc(ll) acetate dihydrate (86 mg, 0.4 mmol) were combined in methanol (5 mL) and refluxed for 30 min, after cooling to room temperature sodium hexafluorophosphate (65 mg, 0.4 mmol) was added and the pale yellow solution filtered and left on the bench to evaporate slowly. White crystals formed after 3 days that were dried in air (85 mg, 54.8 %). 

CH3HL5 (50 mg, 0.09 mmol) and zinc(II) acetate dihydrate (42 mg, 0.19 mmol) were combined in methanol (5 mL) and refluxed for 30 min, after cooling to room temperature sodium hexafluorophosphate (48 mg, 0.29 mmol) was added and the pale yellow solution filtered and left on the bench to evaporate slowly. A white powder was obtained after 3 days which was dried in air (29 mg, 37 %). Crystals suitable for X-ray structure analysis were obtained with the following method CH3HL5 (30 mg, 0.05 mmol) and zinc(II) acetate dihydrate (25 mg, 0.11 mmol) were combined in methanol (3 mL) and refluxed for 30 min, after cooling to room temperature sodium tetraphenylborate (59 mg, 0.17 mmol) was added and the pale yellow solution filtered and left on the bench to evaporate slowly. The white powder was taken up in acetone/isopropanol and layered with hexane which yielded colorless crystals which desiccated readily upon removal from the solvent. X-ray structure analysis was thus conducted with copper radiation at 150 K. Further analysis was done with the hexafluorophosphate derivative. 

The Zn(II) complexes were typically synthesized by adding two equivalents of zinc(ll) acetate dUiydrate dissolved in a small amount of methanol to a ligand solution in methanol and refluxing the mixture for 30 min to ensure complete binding of two equivalents of Zn(ll) to the ligands. Sodium hexafluorophosphate was employed as counter ion as it proved to be the most successful anion for obtaining crystals suitable for X-ray structure determination (Fig. 4.5). 

Cl1H1gFgMoNOP, Bis-7r-cyclopentadienylhydroxymethylaminomolybdenum-(IV) hexafluorophosphate, 40B, 742 C1iH1gB20NbZn 0,5 CgHg, [Carbonylbis(r -cyclopentadienyl)-niobiurn]-M hydrido-[bis(tetrahydridoborato)zinc] benzene solvate, 45B, 945... 

Tetrathiafulvalenes and Selenium Analogues. A review on organic metals has been published. The photoelectron spectra of tetrathiafulvalene (388) and the corresponding di- and tetra-selenium compounds have been determined " and the H n.m.r. spectra of tetrathiafulvalene in nematic liquid-crystalline solvents have been measured. Synthetic procedures for symmetrically substituted tetrathiafulvalenes include the reduction of 1,3-dithiolium hexafluorophosphate with zinc dust, the reductive coupling of l,3-dithiole-2-thiones [cf. (379)] with derivatives of tervalent phosphorus, and a five-stage synthesis of tetraethyl-tetrathiafulvalene, starting from the dithiocarbamate (389). Treatment of a mixture of the dithiolium salts (390 R, R = H, Me, or Et) and (391) with triethylamine results in three products, two symmetrical tetrathiafulvalenes and the crossed compounds (392). The conversion of the bisdithiolone (393) into... 

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