Alkali metal boronates

Like the alkali metal, boron and aluminium hydride compounds, hydroorganosilanes are so polarised that the electron cloud is concentrated on the hydrogen atom, which aids the formation of the hydride anion. Combinations of hydroorganosilanes with organic and inorganic acids or with certain catalysts (the transition metal complexes, the peroxides, etc.), are especially suitable for the reduction of organic compounds. The relative ease of hydride anion formation follows this series [537, 538] ... 

The most common catalysts in order of decreasing reactivity are haUdes of aluminum, boron, zinc, and kon (76). Alkali metals and thek alcoholates, amines, nitriles, and tetraalkylureas have been used (77—80). The largest commercial processes use a resin—catalyst system (81). Trichlorosilane refluxes in a bed of anion-exchange resin containing tertiary amino or quaternary ammonium groups. Contact time can be used to control disproportionation to dichlorosilane, monochlorosilane, or silane. 

Lewis acids are defined as molecules that act as electron-pair acceptors. The proton is an important special case, but many other species can play an important role in the catalysis of organic reactions. The most important in organic reactions are metal cations and covalent compounds of metals. Metal cations that play prominent roles as catalysts include the alkali-metal monocations Li+, Na+, K+, Cs+, and Rb+, divalent ions such as Mg +, Ca +, and Zn, marry of the transition-metal cations, and certain lanthanides. The most commonly employed of the covalent compounds include boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. Various other derivatives of boron, aluminum, and titanium also are employed as Lewis acid catalysts. 

Boron enflames in contact with IF3 so do P, As and Sb. Molybdenum and W enflame when heated and the alkali metals react violently. KH and CaC2 become incandescent in hot IF3. However, reaction is more sedate with many other metals and non-metals, and compounds such as CaCOs and Ca3(P04)2 appear not to react with the liquid. 

The formation of alkali-metal borides by direct synthesis requires temperatures of 750-1200°C, depending on the variety of boron utilized and the specific metal. This leads to two important consequences ... 

Since the synthesis temperatures are higher than the dissociation temperatures of the phases that are formed (at a pressure of lO N m ), it is necessary to react the alkali metal with boron under metal pressure in excess of that defined by Eq. (a), in sealed vessels. The alkali metal is present as a liquid in equilibrium with the vapor phase, the pressure of which is determined by the T of the coldest point. This pressure (greater the more volatile the metal) favors the synthetic reaction relative to the reverse dissociation reaction. 

The reactivity of alkali metals with B decreases as their atomic number increases Li reacts completely with B at 700°C, whereas with K the reaction is not complete until 1200°C, at which T the pressure of the alkali metal is ca. 20 x 10 N m . These pressures demand the use of thick-walled reaction vessels. The boron-alkali metal mixture is placed in a Mo crucible inside such a container made of Fe or Mo, depending on the reaction T. 

The parameters controlling the synthesis are the temperature, the vapor pressure of the alkali metal and the crystalline state of boron. The reactions are unaffected by the atomic ratio, M/B, provided it is much larger than the M/B ratios characteristic of the phases that are to be prepared values of, e.g., ca. 1 /2, 1 or 2, are satisfactory. 

The reduction of a transition-metal oxide and boron oxide by an electropositive metal such as Al, Mg or an alkali metal has been used as a pathway to titanium, iron, chromium, tungsten and alkali-earth borides . ... 

Brown, H. C., The Reactions of Alkali Metal Hydrides and Boro-hydrides with Lewis Acids of Boron and Aluminum, Congr. Lect., 17th Int. Congr. Pure Appl. Chem. p. 167. Butterworths, London, 1960. 

Copper oxides give rise to numerous accidents. When copper (II) oxide was heated with boron, it gave a highly violent reaction, which caused the melting of the Pyrex container. This is true for alkali metals and titanium as well as aluminium. The reactions lead to liquid metal copper. The emissions of glowing compounds make the reaction very dangerous. 

During the time of the Olin reports, the first examples of oligomeric boron-bridged (l-pyrazolyl)borate systems appeared from the laboratory of Trofimenko at DuPont Chemicals 24 He reported the synthesis of poly(l-pyrazolyl)borates (6) (Fig. 5) from the reactions of alkali metal borohydrides with the pyrazole ligand. The (l-pyrazolyl)borate ligand was obtained from two pyrazole units when bridged by a BR2 unit on one side and by a metal or onium ion on the other. Even though reports... 

Between 1965 and 1969, there were rapid developments in the use of other high temperature species, particularly the silicon dihalides (22-23). boron monofluoride (24), boron atoms (25). silicon atoms (26), and alkali metal atoms (27-28). in reactions at liquid nitrogen temperatures. Clearly this experimental method had to be applied to... 

Some of the investigations carried out in the first half of the twentieth century were related to CL associated with thermal decomposition of aromatic cyclic peroxides [75, 76] and the extremely low-level ultraviolet emission produced in different reaction systems such as neutralization and redox reactions involving oxidants (permanganate, halogens, and chromic acid in combination with oxalates, glucose, or bisulfite) [77], In this period some papers appeared in which the bright luminescence emitted when alkali metals were exposed to oxygen was reported. The phenomenon was described for derivatives of zinc [78], boron [79], and sodium, potassium, and aluminum [80]. 

Another differential reaction is copolymerization. An equi-molar mixture of styrene and methyl methacrylate gives copolymers of different composition depending on the initiator. The radical chains started by benzoyl peroxide are 51 % polystyrene, the cationic chains from stannic chloride or boron trifluoride etherate are 100% polystyrene, and the anionic chains from sodium or potassium are more than 99 % polymethyl methacrylate.444 The radicals attack either monomer indiscriminately, the carbanions prefer methyl methacrylate and the carbonium ions prefer styrene. As can be seen from the data of Table XIV, the reactivity of a radical varies considerably with its structure, and it is worth considering whether this variability would be enough to make a radical derived from sodium or potassium give 99 % polymethyl methacrylate.446 If so, the alkali metal intitiated polymerization would not need to be a carbanionic chain reaction. However, the polymer initiated by triphenylmethyl sodium is also about 99% polymethyl methacrylate, whereas tert-butyl peroxide and >-chlorobenzoyl peroxide give 49 to 51 % styrene in the initial polymer.445... 

Phenylhydrazine Phosgene Phosphine Lead dioxide, oxidizers Aluminum, alkali metals, 2-propanol Air, boron trichloride, bromine, chlorine, nitric acid, nitrogen oxides, nitrous acid, oxygen, silver nitrate... 

A similar type of catalyst including a supported noble metal for regeneration was described extensively in a series of patents assigned to UOP (209-214). The catalysts were prepared by the sublimation of metal halides, especially aluminum chloride and boron trifluoride, onto an alumina carrier modified with alkali or rare earth-alkali metal ions. The noble metal was preferably deposited in an eggshell concentration profile. An earlier patent assigned to Texaco (215) describes the use of chlorinated alumina in the isobutane alkylation with higher alkenes, especially hexenes. TMPs were supposed to form via self-alkylation. Fluorinated alumina and silica samples were also tested in isobutane alkylation,... 

The polyhedral boranes and carboranes discussed above may be regarded as boron clusters in which the single external orbital of each vertex atom helps to bind an external hydrogen or other monovalent atom or group. Post-transition main group elements are known to form clusters without external ligands bound to the vertex atoms. Such species are called bare metal clusters for convenience. Anionic bare metal clusters were first observed by Zintl and co-workers in the 1930s [2-5], The first evidence for anionic clusters of post-transition metals such as tin, lead, antimony, and bismuth was obtained by potentiometric titrations with alkali metals in liquid ammonia. Consequently, such anionic post-transition metal clusters are often called Zintl phases. 

The c-BN phase was first obtained in 1957 [525] by exposing hexagonal boron nitride phase (h-BN) to high pressures and low temperatures. A pressure of more than 11 GPa is necessary to induce the hexagonal to cubic transformation, and these experimental conditions prevent any practical application for industrial purposes. Subsequently, it has been found that the transition pressure can be reduced to approximately 5 GPa at very high temperature (1300-1800°C) by using catalysts such as alkali metals, alkali metal nitrides, and Fe-Al or Ag-Cd alloys [526-528]. In addition, water, urea, and boric acid have been successfully used for synthesis of cubic boron nitride from hexagonal phase at 5-6 GPa and temperature above 800-1000°C [529]. It has been... 

A quite new type of antibiotic and one of the few naturally-occurring boron compounds is boromycin (86). Hydrolytic cleavage of D-valine with the M(7) hydroxides gave caesium and rubidium salts of this antibiotic, and crystal structure analysis established the formula as (XIIT). The rubidium ion is irregularly coordinated by eight oxygen atoms. Experiments with models showed that the cation site would be the natural place for the—NH3+ end of the D-valine residue, and the whole structure raises the possibility that transport of larger alkali metals is related to the N-ends of peptides and proteins. 

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