With metal halides chlorides

The zinc chloride is acting here as a Lewis acid. Similarly, thiirane dioxides react with metal halides such as lithium and magnesium chlorides, bromides and iodides in ether or THF to give the halo-metal sulfmates (130) in fair yields157. 

The donor properties of N3P3CI6 appear to be too weak to allow complex formation with metal halides, but it has been reported that complex formation between N3P3Cl5 NHBu" and Cu" or Co" chlorides in acetonitrile solutions can be detected by u.v. spectroscopy. Attempts to isolate the complexes were unsuccessful. 

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. 

Researchers at Solvay reported in a patent that aluminum trichloride can be activated with metal halides [e. g., silver chloride or iron(III) chloride] and acid salts NaF nllF.33 Thus, 1,2-dichloro-l.l,2-trifluoroethane (19) has been converted into 2,2-dichloro-l.l.Ttrifluoroethane (20), and l,1.2-trichloro-l,2.2-trifluoroethane (1) into l.1.l-trichloro-2.2.2-trifluoroethane (2) with reduced byproduct formation. 

Stabilised diazo compounds can be prepared (a) as diazonium sulphates or chlorides, e.g., tetrazotised, o-dianisidine, (b) as complex salts with metallic halides, e.g., RN2C1, ZnCl2, (c) as diazoaryl sulphonates,... 

Enol silyl ethers can lead to a-chloro ketones on treatment with anhydrous copper(II) chloride in DMF or iron(lll) chloride in acetonitrile (equation 13, Table 1). The chlorination of (36 equation 14) proceeds through a cation radical intermediate formed by an electron-transfer process with metal halides. 

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) ... 

Homoleptic allyl complexes and their derivatives are prepared by reacting allylmag-nesium chloride with metal halides . 

Reactions of Grignard reagents with metal halides, usually chlorides or bromides, have been extensively used for the preparation of symmetrical triorganoantimony and... 

Reaction of thiols or thiolates with acyl halides, chlorides in particular, represents the standard method for preparing thiol carboxylic esters (c/. ref. 33 and the literature cited therein). Since thiols ate strong nucleophiles, the acylation even takes place in the absence of base. However, to obtain excellent yields under mild conditions, tertiary amines are added or metal (Si, Sn, T1 Cu ) derivatives of the thiols are used. The following examples demonstrate the scope of the method. 

By far the most frequently used method is the deprotonation with potassium tert-butoxide, which gives the potassium salts in nearly quantitative yields. The method seems to be usable for any bis(chalcogenophosphinyl and -phosphoryl)imide and has been employed for a broad diversity of derivatives, regardless of the nature of the chalcogen.2,26,30,33,36-38,49,89,91,99 If the salts are needed for further use in reactions with metal halides to form complexes, the potassium salt can be used in situ, without isolation, e.g., with zinc(II) chloride or palladium and platinum chloro complexes.41,43 Potassium metal in THF also forms the salt K[SPh2PNPPh2S] in 82% yield, 38 but the method is not practical for preparative purposes. Potassium-crown ether complexes, [K(18-crown-6)][Q1Ph2PNPPh2Q1] with Q1 = O,92 Q1 = S,93 and Q1 = Se,98 have been prepared by direct complexation of the potassium salt with the macrocyclic ligand. 

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... 

Initiation with acid chlorides complexed with metal halides (or silver salts) has been used 17), e.g. ... 

Pyridine is a tertiary amine its aqueous solution shows an alkaline reaction and precipitates the hydroxides of metals, some of which are soluble in an excess of the amine. Salts of pyridine like those of other amines form characteristic double salts with metallic halides. The ferrocyanide of pyridine and the addition-product of pyridine and mercuric chloride are difficultly soluble in water these compounds are used in the purification of the base. Pyridine is a very stable compound it can be heated with nitric acid or chromic acid without undergoing change but at 330° it is converted by a mixture of nitric acid and fuming sulphuric acid into nitropyridine, a colorless compound that melts at 41° and boils at 216°. At a high temperature pyridine is converted into a sulphonic acid by sulphuric acid. Chlorine and bromine form addition-products, e.g., C5H5N.CI2, at the ordinary temperature when these are heated to above 200°, substitution-products are formed. The hydroxyl derivative of pyridine is made by fusing the sulphonic acid with sodium hydroxide it resembles phenol in chemical properties. The three possible carboxyl derivatives of pyridine are known. The a-acid is called picolinic acid, the jS-acid nicotinic acid (664), and the 7-acid isonicotinic acid. 

Cyclobutene, cyclopentene, and norbomene also give their polyalken-amers (64). The molecular weights are all high, and the stereochemistries are largely cis. Of these, cw-polypentenamer has also been made with molybdenum, tungsten, and rhenium halide catalysts, and cii-polynor-bomenamer (of lower molecular weight) with a molybdenum chloride catalyst, but polybutenamer made with metal halide catalysts (the metals tried were Ti, Mo, W, V, Cr, and Ru) has never been found to have more than 60% of its double bonds cis (64). 

As well as readily exchanging cations in aqueous solution, it has been found that ion exchange also occurs upon bringing a cationic zeolite in contact with a metal salt, typically a chloride, and heating the intimate mixture. In particular, Beyer and co-workers have followed the reaction of protonated or ammonium forms of zeolites with metal halides (particularly volatile halides) at elevated temperatures (Scheme 6.5)." This results in hydrogen chloride and ammonium chloride removal and proton exchange by the metal cations. Many such examples have been reported, including zinc, iron(II) and lanthanum into zeolites Y, mordenite and ZSM-5. 

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