Ammonia adduct with

Silver fluoride forms explosive adducts with ammonia (qv) (5,6), and therefore all of the reactions involving Hquid or gaseous ammonia should be carried out with extreme precautions. 

It melts at 39°C and may be purified by vacuum sublimation. The Hquid boils at 233°C to give a monomeric vapor in which the Ti—Br distance is 231 pm. Titanium tetrabromide is soluble in dry chloroform, carbon tetrachloride, ether, and alcohol. Like titanium tetrachloride, TiBr forms a range of adducts with molecules such as ammonia, amines, nitrogen heterocycles, esters, and ethers. 

The majority of U(V1) coordination chemistry has been explored with the trans-ddo s.o uranyl cation, UO " 2- The simplest complexes are ammonia adducts, of importance because of the ease of their synthesis and their versatihty as starting materials for other complexes. In addition to ammonia, many of the ligand types mentioned ia the iatroduction have been complexed with U(V1) and usually have coordination numbers of either 6 or 8. As a result of these coordination environments a majority of the complexes have an octahedral or hexagonal bipyramidal coordination environment. Examples iuclude U02X2L (X = hahde, OR, NO3, RCO2, L = NH3, primary, secondary, and tertiary amines, py n = 2-4), U02(N03)2L (L = en, diamiaobenzene n = 1, 2). The use of thiocyanates has lead to the isolation of typically 6 or 8 coordinate neutral and anionic species, ie, [U02(NCS)J j)/H20 (x = 2-5). 

Zirconium tetraiodide is the least thermally stable zirconium tetrahaUde. At 1400°C, it disproportionates to Zr metal and iodine vapor. This behavior is utilized in the van Arkel-de Boer process to refine zirconium. As with the tetrachloride and tetrabromide, the tetraiodide forms additional adducts with gaseous ammonia which, upon heating, decompose through several steps ending with zirconium nitride. 

Chloral forms well-crystallized adducts (126) with diaziridines containing at least one NH group (B-67MI50800). Carbonyl addition products to formaldehyde or cyclohexanone were also described. Mixtures of aldehydes and ammonia react with unsubstituted diaziridines with formation of a triazolidine ring (128). Fused diaziridines like (128) are always obtained in ring synthesis of diaziridines (127) from aldehyde, ammonia and chloramine. The existence of three stereoisomers of compounds (128) was demonstrated (76JOC3221). Diaziridines form Mannich bases with morpholine and formaldehyde (64JMC626), e.g. (129). 

The most satisfactory route to the synthesis of the ri -borole complexes is the reaction of dihydroboroles (2-borolenes and 3-borolenes) with metal carbonyls. An alternative method of synthesis includes formation of the borole adducts with ammonia, 320 (R = Me, Ph) [87JOM(336)29]. Thermal reaction of 320 (R = Me, Ph) with M(C0)6 (M = Cr, Mo, W) gives 321 (M = Cr, R = Me, Ph M = Mo, W, R = Ph). There are data in favor of the Tr-electron delocalization over the borole... 

The simplest type of Lewis acid-base reaction is the combination of a Lewis acid and a Lewis base to form a compound called an adduct. The reaction of ammonia and trimethyl boron is an example. A new bond forms between boron and nitrogen, with both electrons supplied by the lone pair of ammonia (see Figure 21-21. Forming an adduct with ammonia allows boron to use all of its valence orbitals to form covalent bonds. As this occurs, the geometry about the boron atom changes from trigonal planar to tetrahedral, and the hybrid description of the boron valence orbitals changes from s p lo s p ... 

A good example is B (0113)3 which uses a vacant 2 p orbital to form an adduct with ammonia. The elements in the p block beyond the second row of the periodic table have empty valence d orbitals that allow them to act as Lewis acids. The silicon atom in Sip4 is an example. 

The reactions of boron trifluoride adducts of ammonia,and primary, secondary, and tertiary amines with phosphorus pentachloride have been studied and in the first two cases acyclic phosphazenes were obtained. With the ammonia-adduct, a previously characterized phosphazene salt was obtained ... 

Ammonia reacts with boron trichloride to form a molecule called an adduct or Lewis acid base complex in which the lone pair on the ammonia molecule is shared with the boron atom to form a covalent bond and completing an octet on boron (Figure 1.16) ... 

Ammonia itself yields imines, R2C=NH, with carbonyl compounds but these derivatives are unstable and react with each other to form polymers of varying size. The classical aldehyde ammonias are found to be hydrated cyclic trimers, but from aldehydes carrying powerfully electron-withdrawing substituents it is possible to isolate the simple ammonia adduct [73, cf. (72), and hydrates, p. 208, hemi-acetals,... 

The compound and its adduct with ammonia explode very easily with heat or shock. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

At the outset of our studies of the reactivity of I and II, it was necessary to investigate claims that tertiary henzamides were inappropriate substrates for the Birch reduction. It had been reported that reduction of A,A-dimethylbenzamide with sodium in NH3 in the presence of tert-butyl alcohol gave benzaldehyde and a benzaldehyde-ammonia adduct. We formd that the competition between reduction of the amide group and the aromatic ring was strongly dependent on reaction variables, such as the alkali metal (type and quantity), the availability of a proton source more acidic than NH3, and reaction temperature. Reduction with potassium in NH3-THF solution at —78 °C in the presence of 1 equiv. of tert-butyl alcohol gave the cyclohexa-1,4-diene 2 in 92% isolated yield (Scheme 3). At the other extreme, reduction with lithium in NH3-THF at —33 °C in the absence of tert-butyl alcohol gave benzaldehyde and benzyl alcohol as major reaction products. ... 

The use of ethylene adduct lb is particularly important when the species added to activate catalyst la is incompatible with one of the reaction components. Iridium-catalyzed monoallylation of ammonia requires high concentrations of ammonia, but these conditions are not compatible with the additive [Ir(COD)Cl]2 because this complex reacts with ammonia [102]. Thus, a reaction between ammonia and ethyl ciimamyl carbonate catalyzed by ethylene adduct lb produces the monoallylation product in higher yield than the same reaction catalyzed by la and [Ir(COD)Cl]2 (Scheme 27). Ammonia reacts with a range of allylic carbonates in the presence of lb to form branched primary allylic amines in good yield and high enantioselectivity (Scheme 28). Quenching these reactions with acyl chlorides or anhydrides leads to a one-pot synthesis of branched allylic amides that are not yet directly accessible by metal-catalyzed allylation of amides. 

In the presence of excess ammonia, the surface complex coexists with its ammonia adduct ](=SiO)2Ta(=NH)(NH2)(NH3)]. NMR studies on the fuUy N-labeled samples have led to unambiguous discrimination between imido, amido and amino resonances of the surface complex and its NH3 adduct, and [=Si- NH2] through the combination of soHd-state magic-angle spinning(MAS), heteronuclear correlation (HETCOR), 2D proton double-quantum (DQ), singlequantum (SQ) correlation, and 2D proton triple quantum (TQ) single quantum... 

Reaction with hypochlorite solution also produces chloramine. Ammonia reacts with iodine to form nitrogen triiodide, which further combines with a molecule of NH3 to form an adduct NI3 NH3, an insoluble brown-black sohd which decomposes upon exposure to light in the presence of NH3 ... 

When added to a dilute solution of caustic soda or caustic potash, it forms [Sb(OH)6] ion in the solution, from which the sodium or potassium salt, NaSb(OH)e or KSb(OH)6 crystaUizes out. It forms two adducts with ammonia, a red triammine, SbCls 3NHs, and a colorless tetraammine, SbCls 4NHs. SbCls dissociates on heating to trichloride and chlorine dissociation comenc-ing around 120°C and completing at 300°C. 

Manganese(II) chloride forms adducts with ammonia, hydroxylamine and many other nitrogen compounds. Many adducts are stable at ordinary temperatures. Examples are MnCb BNHs and MnCE 2NH2OH. 

Many 1-alkynes can be prepared in high yields by adding bromine to 1-alkenes and subsequently treating the adduct with three equivalents of alkali amide in liquid ammonia the 1-alkyne is liberated (after removal of the ammonia) by addition of water. 

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