With metal halides fluorides

Most pulmonary agents produce corrosive decomposition products that may include hydrogen chloride (HC1), hydrogen bromide (HBr), hydrogen fluoride (HF), and/or hydrogen cyanide (HCN). Agents with metal halide additives will also form potentially toxic metallic oxides. 

Sulfuric acid reacts with metal halides to form hydrogen halides. Thus, hydrogen fluoride is commercially made by the action of calcium fluoride with the acid ... 

JCS 1948, 2135-38 (Reaction of bromine tri-fluoride with metallic halides) 58)J.Prat,... 

Zirconium and hafnium tetrahalides form a variety of double halides with metal halides. The most widespread composition is Q2MX6 (Q = monovalent cation) but the QMX5 complexes and fluoride complexes Q3MF7 and Q4MF8 are also documented. Q2MX6 chlorides and bromides consist of [MXe] octahedra. The complex chloride anions [MCls]" and [MCle]" have been detected in molten MCI4 (equation 15) ... 

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... 

Organolithium reagents (Section 14 3) Lithi um metal reacts with organic halides to pro duce organolithium compounds The organic halide may be alkyl alkenyl or aryl Iodides react most and fluorides least readily bro mides are used most often Suitable solvents include hexane diethyl ether and tetrahy drofuran... 

Metal halides react with BF (33) when heated to form BX and the metal fluoride. For example,... 

Complex Halides. Mercuric haUdes (except the fluoride) form neutral complex salts with metallic haUdes. Those made with alkah metal salts frequendy are more soluble in water than the mercuric haUde itself, and take the form of MHgX and M2HgX. ... 

Coupling reactions and related fluoroalkylations with polytTuoioalkyl halides are induced by vanous reagents, among them metals such as copper and zinc, or by an electrochemical cell. More recently, examples of carbon-carbon bond forma tion by coupling of unsaturated fluorides have been reported Both acyclic and cyclic fluoroolefins of the type (Rp)2C=CFRp undergo reducUve dimerization on treatment with phosphines [42] (equation 33) The reaction shown in equation 33 IS also accompbshed electrocheimcally but less cleanly [43]... 

Metal halides can in some cases, be used to replace other atoms or groups besides fluorine with halogen Polyfluoroacyl fluorides and chlorides can be converted to fluoroalkyl iodides by simply heating the reactant in the presence of an alkali metal iodide [[Pg.382]

There is also clear evidence of a change from predominantly class-a to class-b metal charactristics (p. 909) in passing down this group. Whereas cobalt(III) forms few complexes with the heavier donor atoms of Groups 15 and 16, rhodium(III), and more especially iridium (III), coordinate readily with P-, As- and S-donor ligands. Compounds with Se- and even Te- are also known. Thus infrared. X-ray and nmr studies show that, in complexes such as [Co(NH3)4(NCS)2]" ", the NCS acts as an A -donor ligand, whereas in [M(SCN)6] (M = Rh, Ir) it is an 5-donor. Likewise in the hexahalogeno complex anions, [MX ] ", cobalt forms only that with fluoride, whereas rhodium forms them with all the halides except iodide, and iridium forms them with all except fluoride. 

Numerous compounds adopt the PbFCl structure. These include, apart from fluoride chlorides, oxide halides MOX (M = Bi, lanthanoids, actinoids X = Cl, Br, I), hydride halides like CaHCl and many compounds with metallic properties like ZrSiS or NbSiAs. 

It reacts even more vigorously with most substances than does cobalt fluoride. See other metal halides, silver compounds... 

Main-group elements X such as monovalent F, divalent O, and trivalent N are expected to form families of transition-metal compounds MX (M—F fluorides, M=0 oxides, M=N nitrides) that are analogous to the corresponding p-block compounds. In this section we wish to compare the geometries and NBO descriptors of transition-metal halides, oxides, and nitrides briefly with the isovalent hydrocarbon species (that is, we compare fluorides with hydrides or alkyls, oxides with alkylidenes, and nitrides with alkylidynes). However, these substitutions also bring in other important electronic variations whose effects will now be considered. 

Extension of the method to nonisostructural metal halides, some of which yield erroneous AHf values via Bom-Haber cycles, is shown in Fig. 1. All curves are nonlinear with the bow increasing in the expected order T1(I) < Pb(II) < Bi(III) < Ag(I). For the first transition metal dihalides, however, straight lines can be drawn within the limits of enthalpy errors except for Zn(II) or Mn(II) salts. Thus heats of formation of the fluorides can be extrapolated linearly from the other three halides to a first approximation. 

Fluorinated and Chlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The literature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl halides, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal halide catalysts, such as... 

CsCl HgCl2=3 1, 2 1, 1 1, 2 3, 1 2, and 1 5 and five caesium antimonious fluorides where CsF SbF3=l 1, 3 4, 4 7, 1 2, and 1 3. According to I. Remsen s rale (1889) When a halide of any element combines with a halide of an alkali metal to form a double salt, the number of molecules of the alkali salt which are added to one molecule of the other halide is never greater, and is generally less than the number of halogen atoms contained in the latter—for instance, in the double fluoride of sodium and aluminium, where the negative halide has three fluorine atoms, no more than three molecules of sodium fluoride will be found united with one of aluminium fluoride. 

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