Palladium tetrafluoride

Manganese trichloride oxide, 4141 Manganese trifluoride, 4335 Mercury(II) bromide, 0269 Mercury(I) fluoride, 4312 Mercury(II) iodide, 4602 Molybdenum hexafluoride, 4365 Molybdenum pentachloride, 4180 Neptunium hexafluoride, 4366 Osmium hexafluoride, 4370 Palladium tetrafluoride, 4347 Palladium trifluoride, 4341... 

Palladium(II) acetate, 1536 Palladium(II) azide, 4777 Palladium(II) azidodithioformate, 1011 Palladium(III) oxide, 4842 Palladium(II) oxide, 4819 Palladium(IV) oxide, 4829 Palladium, 4879 Palladium tetrafluoride, 4341 Palladium trifluoride, 4335 Paraformaldehyde, 0416 Pentaammmeaquacobalt(III) chlorate, 4118... 

Osmium hexafluoride, 4364 Palladium tetrafluoride, 4341 Palladium trifluoride, 4335... 

Although the linking through fluorine bridges is different from that in palladium tetrafluoride, the fluorine atom positions in vanadium tetrafluoride correspond approximately to a hexagonal close-packed array. The linking of octahedra leads to a complex layer structure, rather than the three-dimensional lattice of the palladium tetrafluoride arrangement. 

This suggests that selenium tetrafluoride is able to act as a fluoride-ion donor and that the adduct with palladium tetrafluoride is the salt (SeF3+)2[PdFg]2 . Since the platinum tetrafluoride and germanium tetrafluoride adducts are isomorphous with the palladium P compound they should also be given the ionic formulation. 

NEW FLUORIDES OF PALLADIUM PALLADIUM (n) HEXAFLUOROPALLADATE (iv) AND RELATED COMPOUNDS AND PALLADIUM TETRAFLUORIDE... 

A Neutron Powder Diffraction Study of Palladium Tetrafluoride... 

N. Bartlett and P. R. Rao, New Fluorides of Palladium Palladium(II) Hexafluoro-palladate(IV) and Related Compounds and Palladium Tetrafluoride, Proc. Chem. Soc. 

A. F. Wright, B. E. F. Fender, N. Bartlett and K. Leary, A Neutron Powder Diffraction Study of Palladium Tetrafluoride, Inorg. Chem. 17 (1978) 748-749. 

Unlike nickel catalysts, palladium catalysts undergo neither cyclodimerization nor cyclotrimerization to form COD or CDT. Only one paper by Chepaikin and Khidekel reported that a mixture of divinylcyclobu-tanes was obtained from butadiene using palladium salts with noncom-plexing anions such as perchlorate and boron tetrafluoride (15). This is a big difference between the catalyses of palladium and nickel. 

Although the number of tetrafluorides reported is as large as the number of di- and trifluorides (see Table III), this group of compounds is the least well characterized structurally of the transition metal fluorides. The synthesis of most of the expected tetrafluorides has been reported, with examples from titanium to manganese in the first, from zirconium to palladium (except for technetium) in the second, and from hafnium to platinum (except for tantalum) in the third series. Many of them have been little studied and, in general, they have not proved amenable to crystallographic structural analysis. 

There are two fluorination reactions with ester substrates reported in the literature which consist of only a single example each. One is the formation of fluoroethene from acetoxyethene and lithium fluoride in the presence of palladium acetate. The other is formation of fluoro-ethane from ethyl orthoformate with silicon tetrafluoride. - ... 

Essentially the same route as that of Ruff has been followed by us, except that two new reducing agents whose chemistry is under study in these laboratories, namely sulphur and selenium tetrafluorides, have been used. Attention has already been drawn to the usefulness of selenium tetrafiuoride as a mild reducing agent in fluorine chemistry while sulphur tetrafiuoride also gives evidence of possessing similar properties. In the first series of experiments, palladium trifluoride, formed by the reaction between palladous iodide and elementary fluorine at room temperature, was treated with a stream of sulphur tetrafluoride at 250-300°. The violet-coloured powder which resulted was proved, by Af-ray examination, to contain palladium difluoride in admixture with about 10% of palladium metal. 

PdF, was prepared by the reduction of palladia fluoride with seleniiun tetrafluoride and the sample was heated in the tetrafluoride vapour at 280 °C. for 30 minutes. This temperature is somewhat higher than that used for the preparation of pure samples of the difluoride (which were imfortunately poorly crystalline) and the resulting material contained a small quantity of palladium metal. Since palladous fluoride is hydrolysed in moist air, thin walled X-ray specimen capillaries, 0-5 nun. diameter (supplied by Pantak Ltd, Slough) were filled and sealed off in a dry box. 

The tetrafluorides of iridium, rhodium and palladium [13] have been established by the work reported in this paper and together with Ptp4 constitute a structurally related set. 

N. Bartlett and J. W. Quail, The Preparation of Palladium Difluoride and Complex Fluorides of Palladium in Selenium Tetrafluoride, J. Chem. Soc. (1961) 3728-3732. 

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