Boron halides determination

Although they are not classified as organoboron compounds, boron hydrides, chloroboranes, boron halides and boric acid esters are discussed in the first part of this chapter as also is the determination of hydridic and active hydrogen in these types of compounds. 

With boron and an appropriate amount of some sort of alkaline metal halide present in the starting materials for the solid-state reactions, then we obtain zirconium cluster materials belonging to the 6-14 family. Single-crystal X-ray data of products from iodine-rich reactions were used to determine the crystal structures of Na[(Zr6B)Cl3.87(5)lio.i3], and Cs[(Zr6B)Cl2.i6(5)lii.84] [21]. Both phases... 

The overall mechanism is closely related to that of the other cross-coupling methods. The aryl halide or triflate reacts with the Pd(0) catalyst by oxidative addition. The organoboron compound serves as the source of the second organic group by transmetala-tion. The disubstituted Pd(II) intermediate then undergoes reductive elimination. It appears that either the oxidative addition or the transmetalation can be rate-determining, depending on reaction conditions.134 With boronic acids as reactants, base catalysis is normally required and is believed to involve the formation of the more reactive boronate anion.135... 

The strength or coordinating power of different Lewis acids can vary widely against different Lewis bases. Thus, for example, in the case of boron trihalides, boron trifluoride coordinates best with fluorides, but not with chlorides, bromides, or iodides. In coordination with Lewis bases such as amines and phosphines, BF3 shows preference to the former (as determined by equilibrium constant measurements).66 The same set of bases behaves differently with the Ag+ ion. The Ag+ ion complexes phosphines much more strongly than amines. In the case of halides (F, CP, Br, and P), fluoride is the most effective base in protic acid solution. However, the order... 

The Suzuki coupling reaction is a powerful tool for carbon-carbon bond formation in combinatorial library production.23 Many different reaction conditions and catalyst systems have been reported for the cross-coupling of aryl triflates and aromatic halides with boronic acids in solution. After some experimentation, we found that the Suzuki cleavage of the resin-bound perfluoroalkylsulfonates proceeded smoothly by using [l,l -bis (diphenylphosphino)ferrocene]dichloropalladium(II), triethylamine, and boronic acids in dimethylformamide at 80° within 8 h afforded the desired biaryl compounds in good yields.24 The desired products are easily isolated by a simple two-phase extraction process and purified by preparative TLC to give the biaryl compounds in high purity, as determined by HPLC, GC-MS, and LC-MS analysis. 

Most of the mechanistic work on this reaction has been devoted to determining the role of the base. Its most obvious function would be to complex the Lewis-acidic boron reagent, rendering it nucleophihc and thus activating it toward transmetallation. However, Miyaura, Suzuki, and coworkers noted that an electron-rich tetracoordinate boronate complex was less reactive than a bivalent boronic ester. From this, they surmised that the role of the base was not to activate the boron toward transmetallation, but rather to transform the palladium halide intermediate to the hydroxide or alkoxide species, which would then be more reactive toward boron. However, in a mass spectrometry study of a reaction between a pyridyl halide substrate and an aryl boroiuc acid, Aliprantis and Canary saw no evidence of palladium hydroxide or alkoxide intermediates, despite observing signals in the mass spectra assignable to every other palladium intermediate of the proposed catalytic cycle. ... 

Other Lewis acids that complex with thietane are titanium tetrachloride or bromide,boron trifluoride,trimethylaluminum, and tin tetrachloride. The enthalpies of formation of the aluminum complex (— 16.04 kcal/mole) and the tin complex (— 14.2 kcal/mole) and the wavelength of the charge transfer band of the tin complex (270 nm) have been determined. The titanium tetrahalides form both a 1 1 and a 1 2 adduct (titanium halide thietane). °° Treatment of 3-methyl-thietane with aluminum chloride or tin tetrachloride yields a rubbery white soUd." "... 

This volume has been written for those chemists and biochemists who may never themselves do X-ray diffraction analyses of crystals, but who need to be able to understand the results of such studies on structures of immediate interest to them. The fields of structural biology and chemistry have blossomed in the years since X-ray diffraction was discovered in 1912. For example, the three-dimensional structures of benzene, graphite, the alkali halides, the boron hydrides, the rare gas halides, penicillin, vitamin Bjj, hemoglobin, lysozyme, transfer RNA, and the common-cold rhinovirus have been determined and, in each case, the results have greatly increased our understanding of fundamental chemistry and biochemistry. 

When a sample is dissolved, the phosphorus usually passes into solution as P(V). Rather than isolate the phosphate, it is often better to isolate the interfering elements, leaving the phosphate to be determined in the mother liquor. Examples of such separations include distillation of Si, As, and Ge as volatile halides [1] or of boron as trimethyl borate [2], precipitation of heavy metals as sulphides from an acid medium, retention of cations on a strongly acidic cation exchanger, and electrolytic separation of metals. 

Organoaluminum sonochemistry is not yet well developed despite the synthetic and economic interest. Aluminum, a ductile metal, is easily activated by sonication, as evidenced by the use of foils to determine the energy of cleaning baths. Alkyl halides react with aluminum at room temperature in THF to give the sesquihalide, reduced to the trialkyl compound in the presence of magnesium. Examples are known with bromomethane or -ethane.1 2,183 reaction occurs with stirring under similar conditions. Triethylaluminum was used in sonochemical transmetallation reactions leading to zinc and boron alkyls (Eq. 38). 

---