Metal carbonyls fluorides

Uses. Besides polymerizing TFE to various types of high PTEE homopolymer, TEE is copolymerized with hexafluoropropylene (29), ethylene (30), perfluorinated ether (31), isobutylene (32), propylene (33), and in some cases it is used as a termonomer (34). It is used to prepare low molecular weight polyfluorocarbons (35) and carbonyl fluoride (36), as well as to form PTEE m situ on metal surfaces (37). Hexafluoropropylene [116-15-4] (38,39), perfluorinated ethers, and other oligomers are prepared from TEE. 

The xenon fluorides, especially the difluoride, could also be used as calorimetric gases with possible applications for organic fluorides or metal carbonyls [e.g., Mo(CO)6 — Mo(CO)BFg. — MoF ]. 

Nitroarenes are reduced to anilines (>85%) under the influence of metal carbonyl complexes. In a two-phase system, the complex hydridoiron complex [HFe,(CO)u]2-is produced from tri-iron dodecacarbonyl at the interface between the organic phase and the basic aqueous phase [7], The generation of the active hydridoiron complex is catalysed by a range of quaternary ammonium salts and an analogous hydrido-manganese complex is obtained from dimanganese decacarbonyl under similar conditions [8], Virtually no reduction occurs in the absence of the quaternary ammonium salt, and the reduction is also suppressed by the presence of carbon monoxide [9], In contrast, dicobalt octacarbonyl reacts with quaternary ammonium fluorides to form complexes which do not reduce nitroarenes. 

Hypochlorites are obtained by reaction of fluorinated carbonyl compounds, such as carbonyl fluoride, with an alkali metal fluoride and chlorine fluoride [62, 120]... 

In any of the fluorinated alkoxides made this way there must always be a fluorine attached to the a-carbon. There is in fact an equilibrium between the metal perfluoroalkoxide and the metal fluoride and carbonyl fluoride compound. Thus these Group IA metal alkoxides cannot be used in metathe-tic reactions to prepare other metal alkoxides. For example, R3SiCl and NaOCF(CF3)2 react to yield RjSiF, NaCl and (CF3)2CO rather than R3SiOCF(CF3)2.138... 

The known reactions of fluorinated olefins, arenes, and heterocycles with metal carbonyl anions, to afford fluorovinyl or fluoroaryl complexes resulting from net displacement of fluoride ion (see Section II1,G), prompted us to attempt such substitution reactions with OFCOT, in order to generate the required metal-substituted heptafluorocyclooctatetraenes. 

Versatile synthetic routes are available to prepare metal carbonyl cations in superacidic media. The most successful methods include reductive carbonylation of metal fluorosulfates or fluorides [Eqs. (4.237)1003 and (4.238)1004]-1002 1005 This... 

Carbon tetrafluoride, 1 34 3 178 Carbon tetraiodide, 3 37 Carbonyl azide, formation of, by carbohydrazide, 4 35 Carbonyl fluoride, 6 155 Carbonyls, metal, 2 229 metal, nomenclature of, 2 264 structure of, 2 232 Catalysts, beryllium chloride, 5 25 boron fluoride, 1 23 chromium(III) oxide gel, 2 190... 

The largest proportion of TFE is used for the polymerization into a variety of PITH homopolymers. It is also used as comonomer in the copolymerization with hexaflu-oropropylene, ethylene, perfluorinated ether, and other monomers and also as a comonomer in a variety of terpolymers. Other uses of TFE are to prepare low-molecular-weight polyfluorocarbons, carbonyl fluoride oils, as well as to form PTFE in situ on metal surfaces,13 and in the synthesis of hexafluoropropylene, perfluorinated ethers, and other oligomers.14... 

In operation, the gases enter at diametrically opposite sides of the cylindrical combustion chamber. It is here that much carbonyl fluoride is formed and much heat is liberated. If flow rates are too high, the heat of the reaction may ignite copper in contact with fluorine. The capacity of the apparatus to produce trifluoromethyl hypo-fluorite appears to be limited by the rate of removal of heat from this reactor. A mixing chamber made from copper, nickel. Monel metal, or other fluorine-resistant metal should be satisfactory, provided that adequate provision is made for removal of heat. Suitable rates of flow for the apparatus described are fluorine, about 5 l./hour carbon monoxide, about 2 to 2.3 l./hour. The limiting rates have not been established. It is important that the ratio by volume of fluorine to carbon monoxide be somewhat more than 2 1. 

Silicon hydrides are an interesting class of carbonyl reducing agents as they are reasonably stable under normal conditions requiring activation with a transition metal complex,fluoride ion or Lewis acid. The correct choice of reaction conditions allows highly chemo- and stereo-selective reduction of particular classes of carbonyl compounds with these convenient reagents. 

These compounds may be formed directly from the metal halides by the action of CO (for example, CO and anhydrous C0I2 give Co(CO)l2) or, in the case of iron iiylirectly from the carbonyls or carbonyl hydrides. The only carbonyl fluoride which has been well characterized has the empirical formula Mo(CO)2F4 a dimeric structure with two bridging F atoms has been suggested. The compounds Pt(CO)2p8 and Rh(CO)2p3 have been described as the products of the action of... 

A general patented method [905] for the preparation of tetrahalomethanes has been claimed in which a carbonyl halide of general formula, COXY (X = F, Cl or Br Y = Cl or Br) is combined with a carbonyl fluoride halide, COXF (X = F, Cl or Br) in the presence of an activated carbon cataiyst (containing the halide of a transition metal) at a temperature of 250-1400 C. Thus, heating COBrF in an autociave is claimed to induce the following reaction [902,905] ... 

Other alkenyl complexes have been formed by displacement of fluoride or chloride ion from fluoro-olefins by metal carbonyl anions, by reactions of the perfluoroalkenylsilver derivative with metal halide compounds, and by insertion of an alkyne into a metal-X bond, and parameters are given with structures [168] to [187]. (8, 86-91) As... 

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