Metal ionic hydrogenation

By analogy, ammonium salts should behave as acids in liquid ammonia, since they produce the cation NH4 (the solvo-cation ), and soluble inorganic amides (for example KNHj, ionic) should act as bases. This idea is borne out by experiment ammonium salts in liquid ammonia react with certain metals and hydrogen is given off. The neutralisation of an ionic amide solution by a solution of an ammonium salt in liquid ammonia can be carried out and followed by an indicator or by the change in the potential of an electrode, just like the reaction of sodium hydroxide with hydrochloric acid in water. The only notable difference is that the salt formed in liquid ammonia is usually insoluble and therefore precipitates. 

Barium is a member of the aLkaline-earth group of elements in Group 2 (IIA) of the period table. Calcium [7440-70-2], Ca, strontium [7440-24-6], Sr, and barium form a closely aUied series in which the chemical and physical properties of the elements and thek compounds vary systematically with increa sing size, the ionic and electropositive nature being greatest for barium (see Calcium AND CALCIUM ALLOYS Calcium compounds Strontium and STRONTIUM compounds). As size increases, hydration tendencies of the crystalline salts increase solubiUties of sulfates, nitrates, chlorides, etc, decrease (except duorides) solubiUties of haUdes in ethanol decrease thermal stabiUties of carbonates, nitrates, and peroxides increase and the rates of reaction of the metals with hydrogen increase. 

Finally, a special example of transition metal-catalyzed hydrogenation in which the ionic liquid used does not provide a permanent biphasic reaction system should be mentioned. The hydrogenation of 2-butyne-l,4-diol, reported by Dyson et al., made use of an ionic liquid/water system that underwent a reversible two-... 

The nature of a binary hydride is related to the characteristics of the element bonded to hydrogen (Fig. 14.8). Strongly electropositive metallic elements form ionic compounds with hydrogen in which the latter is present as a hydride ion, H. These ionic compounds are called saline hydrides (or saltlike hydrides). They are formed by all members of the s block, with the exception of beryllium, and are made by heating the metal in hydrogen ... 

Ionic hydrogenations of C=C and C=0 bonds were reported prior to the development of ionic hydrogenations mediated or catalyzed by transition metals. Tri-fluoroacetic acid (CF3C02H) as the proton donor and triethylsilane (HSiEt3) as the hydride donor are most commonly used, though a variety of other acids and several other hydride donors have also been shown to be effective. A review [1] by Kursanov et al. of the applications of ionic hydrogenations in organic synthe-... 

Stoichiometric Ionic Hydrogenations using Transition-Metal Hydrides 7.2.2.1 General Aspects... 

Stoichiometric Ionic Hydrogenation of Alkenes with Metal Hydrides as the Hydride Donor... 

Several systems have been reported involving stoichiometric hydrogenation of ketones or aldehydes by metal hydrides in the presence of acids. An ionic hydrogenation mechanism accounts for most of these hydrogenations, though in some examples alternative mechanisms involving the insertion of a ketone into a M-H bond are also plausible. 

The kinetics of the ionic hydrogenation of isobutyraldehyde were studied using [CpMo(CO)3H] as the hydride and CF3C02H as the acid [41]. The apparent rate decreases as the reaction proceeds, since the acid is consumed. However, when the acidity is held constant by a buffered solution in the presence of excess metal hydride, the reaction is first-order in acid. The reaction is also first-order in metal hydride concentration. A mechanism consistent with these kinetics results is shown in Scheme 7.8. Pre-equilibrium protonation of the aldehyde is followed by rate-determining hydride transfer. 

Stoichiometric Ionic Hydrogenation of Acyl Chlorides to Aldehydes with HOTf/Metal Hydrides... 

Stoichiometric Ionic Hydrogenation of Ketones with Metal Dihydrides... 

Molybdenum and tungsten carbonyl hydride complexes were shown (Eqs. (16), (17), (22), (23), (24) see Schemes 7.5 and 7.7) to function as hydride donors in the presence of acids. Tungsten dihydrides are capable of carrying out stoichiometric ionic hydrogenation of aldehydes and ketones (Eq. (28)). These stoichiometric reactions provided evidence that the proton and hydride transfer steps necessary for a catalytic cycle were viable, but closing of the cycle requires that the metal hydride bonds be regenerated from reaction with H2. 

The use of ionic liquids has been successfully studied in many transition metal-catalyzed hydrogenation reactions, ranging from simple alkene hydrogenation to asymmetric examples. To date, almost all applications have included procedures of multiphase catalysis with the transition-metal complex being immobilized in the ionic liquid by its ionic nature or by means of an ionic (or highly polar) ligand. 

Stoichiometric Ionic Hydrogenations using Transition-Metal... 

Stoichiometric Ionic Hydrogenation of Ketones and Aldehydes using Metal Hydrides as Hydride Donors and Added Acids... 

These forces affect the boiling point, melting point, hardness, and electrical and heat conductivity of a substance. In this chapter, we will study metals, ionic solids, network solids, dipole-dipole attractions, van der Waals forces and hydrogen bonds. 

For each of the substances the possible answers are ionic bonding, covalent bonding, metallic bonding, hydrogen bonding, dipole-dipole force, or London force. Forces, such as ion-dipole forces and ion-induced dipole forces, are not choices because these require the presence of two or more substances. For example, sodium chloride cannot utilize either of these two forces, but sodium chloride in water can. (Sodium chloride in water exhibits ion-dipole forces.)... 

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