Boron-like

BWRs do not operate with dissolved boron like a PWR but use pure, demineralized water with a continuous water quality control system. The reactivity is controlled by the large number of control rods (>100) containing burnable neutron poisons, and by varying the flow rate through the reactor for normal, fine control. Two recirculation loops using variable speed recirculation pumps inject water into the jet pumps inside of the reactor vessel to increase the flow rate by several times over that in the recirculation loops. The steam bubble formation reduces the moderator density and... 

Boron (like silicon) invariably occurs in nature as 0X0 compounds and is never found as the element or even directly bonded to any other element than oxygen. The structural chemistry of B-O compounds is characterized by an extraordinary complexity and diversity which rivals those of the borides (p. 145) and boranes (p. 151). In addition, vast numbers of predominantly organic compounds containing B-O are known. 

Bidentate binding of two Lewis acidic boron centers to one methoxide anion was first reported in 1967 [241]. Further examples did not appear until 1985 [242]. Today, other bis(boronates) like 152 and 154-158 (Fig. 41) are known that can be applied to the selective complexation of amines and diamines [243-247]. 

Boron, like silicon, occurs in nature exclusively as oxy-compounds, particularly hydroxyborates of calcium and sodium. In borates based exclusively on BO3 coordination groups there would be a simple relation between the 0 B ratio and the number of 0 atoms shared by each BO3 group, assuming these to be equivalent and each bonded to 2 B atoms ... 

Boron, like most nonmetals, has acidic oxides. Hydration of B2O3 yields boric acid, H3BO3 or B(0H)3, in which B has an incomplete octet and can therefore act as a Lewis acid ... 

Like bortezomib, MLN9708 is also a peptide boronate (Fig. 13.5) but it is orally active, shows greater tissue penetration, and has a shorter half-hfe. The drug is primarily an inhibitor of the chymotrypsin-like activity of the 20S proteasome core and, like bortezomib, it inhibits NF-kB activation and has antitumor activity in multiple myeloma and some other hematologic mahgnan-cies. Besides peptide boronates like bortezomib, other synthetic compounds tested as proteasome inhibitors include peptide aldehydes, peptide epoxyketones, and peptide vinyl sulfones. 

Boron, like the other electrophiles we have looked at, adds to the sp carbon bonded to the most hydrogens. There are two reasons for the regioselectivity. First, there is more room at this sp carbon for the electrophile to attach itself, because it is the less substituted sp carbon. 

Predictions of [13] also include 2s 2p levels of some ions isoelectronic with O, N, C, B, Be, and Li. The elements Os, Ir, and Pt are not considered, but relevant data can be derived by interpolation. Isoelectronic trends in the n=2 —n=2 transition probabilities are sketched in [14] for boron-like ions by the relativistic parametric potential method and in [15] for beryllium-like ions by a 1/Z perturbation method. In a survey of the lithium-like sequence, Steiger reports spontaneous emission rates and energies for three forbidden transitions of lr + [16]. A relativistic model potential method was used by Gogava etal. for deriving the lowest 15 energy levels of all lithium-like ions [17]. 

The element before carbon in Period 2, boron, has one electron less than carbon, and forms many covalent compounds of type BX3 where X is a monovalent atom or group. In these, the boron uses three sp hybrid orbitals to form three trigonal planar bonds, like carbon in ethene, but the unhybridised 2p orbital is vacant, i.e. it contains no electrons. In the nitrogen atom (one more electron than carbon) one orbital must contain two electrons—the lone pair hence sp hybridisation will give four tetrahedral orbitals, one containing this lone pair. Oxygen similarly hybridised will have two orbitals occupied by lone pairs, and fluorine, three. Hence the hydrides of the elements from carbon to fluorine have the structures... 

Aluminium tetrahydridoborate is a volatile liquid. It is the most volatile aluminium compound known. It is covalent and does not contain ions but has a hydrogen-bridge structure like that of diborane, i.e. each boron atom is attached to the aluminium by two hydrogen bridges ... 

Both boron and aluminium chlorides can be prepared by the direct combination of the elements. Boron trichloride can also be prepared by passing chlorine gas over a strongly heated mixture of boron trioxide and carbon. Like boron trifluoride, this is a covalent compound and a gas at ordinary temperature and pressure (boiling point 285 K). It reacts vigorously with water, the mechanism probably involving initial co-ordination of a water molecule (p, 152). and hydrochloric acid is obtained ... 

It forms an ion BCI4 only under special circumstances, and never in aqueous solutions (cf. BF3). Like the trifluoride, it is an electron pair acceptor, but the adducts formed tend to decompose more readily. Unlike the corresponding aluminium chloride, boron trichloride exists only as the monomer. 

By subjecting boron nitride (a white powder) to high pressure and temperature small crystals of a substance harder than diamond, known as borazon, are obtained. This pressure-temperature treatment changes the structure from the original graphite-like layer structure (p. 163) to a diamond-like structure this hard form can withstand temperatures up to 2000 K. 

The isotope boron-10 is used as a control for nuclear reactors, as a shield for nuclear radiation, and in instruments used for detecting neutrons. Boron nitride has remarkable properties and can be used to make a material as hard as diamond. The nitride also behaves like an electrical insulator but conducts heat like a metal. 

Cations like that present in (iv) exist in solutions of aromatic hydrocarbons in trifluoroacetic acid containing boron trifluoride, and in liquid hydrogen fluoride containing boron trifluoride. Sulphuric acid is able to protonate anthracene at a mero-position to give a similar cation. ... 

A more eflicient and general synthetic procedure is the Masamune reaction of aldehydes with boron enolates of chiral a-silyloxy ketones. A double asymmetric induction generates two new chiral centres with enantioselectivities > 99%. It is again explained by a chair-like six-centre transition state. The repulsive interactions of the bulky cyclohexyl group with the vinylic hydrogen and the boron ligands dictate the approach of the enolate to the aldehyde (S. Masamune, 1981 A). The fi-hydroxy-x-methyl ketones obtained are pure threo products (threo = threose- or threonine-like Fischer formula also termed syn" = planar zig-zag chain with substituents on one side), and the reaction has successfully been applied to macrolide syntheses (S. Masamune, 1981 B). Optically pure threo (= syn") 8-hydroxy-a-methyl carboxylic acids are obtained by desilylation and periodate oxidation (S. Masamune, 1981 A). Chiral 0-((S)-trans-2,5-dimethyl-l-borolanyl) ketene thioketals giving pure erythro (= anti ) diastereomers have also been developed by S. Masamune (1986). 

When a sibcon crystal is doped with atoms of elements having a valence of less than four, eg, boron or gallium (valence = 3), only three of the four covalent bonds of the adjacent sibcon atoms are occupied. The vacancy at an unoccupied covalent bond constitutes a hole. Dopants that contribute holes, which in turn act like positive charge carriers, are acceptor dopants and the resulting crystal is -type (positive) sibcon (Fig. Id). 

Unlike boron, aluminum, gallium, and indium, thallium exists in both stable univalent (thaHous) and trivalent (thaUic) forms. There are numerous thaHous compounds, which are usually more stable than the corresponding thaUic compounds. The thaUium(I) ion resembles the alkaU metal ions and the silver ion in properties. In this respect, it forms a soluble, strongly basic hydroxide and a soluble carbonate, oxide, and cyanide like the alkaU metal ions. However, like the silver ion, it forms a very soluble fluoride, but the other haUdes are insoluble. Thallium (ITT) ion resembles aluminum, gallium, and indium ions in properties. 

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