Halides organoboron

Further (c/. Vol. 1, p. 89) Russian work on fluoroalkenylcarbaboranes has been reported (see p. 60), fluoroalkylborates have been synthesized via reaction of hexafluoroacetone and related ketones with boron halides, organoboron halides, or alkylthioboranes (see p. 257), and from perfluoro-alkyl hypochlorites (see p. 264), CFj-S—B compounds have been prepared (see p. 270), and conductivity studies on the complex acid HBfOaC CFj) and its caesium salt have been described. Attempts to isolate the tristri-fluoroacetate B(02C CF3)a from products of the reaction systems B(OH)3-(CFs CO) , BCl3-(CF9 CO)jO-n-pentane, and BCl3-CF3-C02H-n-pentane have yielded only I(CF3 C0s)2B]20 or [(CF3 C02)2B]30-B(02C CF3)3 mixtures (c/. ref. 58). 

Palladium-catalyzed carbon-carbon bond forming reactions like the Suzuki reac-tion as well as the Heck reaction and the Stille reaction, have in recent years gained increased importance in synthetic organic chemistry. In case of the Suzuki reaction, an organoboron compound—usually a boronic acid—is reacted with an aryl (or alkenyl, or alkynyl) halide in the presence of a palladium catalyst. 

As a further approach for novel electrolytes appropriate for selective cation transport, we have prepared poly(organoboron halide)-imidazole complexes.35 Even though boron-amine complexes are widely known materials reported by the early works of H. C. Brown et al.,52-54 they had not been investigated as solvents or electrolytes to the best of our knowledge. 

The organoboron polymer complex was prepared as follows. First, poly(organoboron halide)55 was prepared according to the reported method, by hydroboration polymerization between 1,7-octadiene and the monobromoborane dimethylsuffide complex. The polymer obtained was then reacted with half an equivalent of methanol and 1-methylimidazole to give the corresponding copolymer efficiently (scheme 4). The structure of the polymer was characterized by H- and UB-NMR spectra. 

It is known that organoboron halide-imidazole complexes dissociate diming equilibrium 56 however, charges disappear upon dissociation. In such a matrix, mobile ions should not originate from the matrix. Therefore, the polymer electrolytes composed of boron halide-imidazole complexes were considered to be appropriate for selective ion transport. 

Figure 5 Temperature dependence of ionic conductivity for poly(organoboron halide)-imidazole complexes in the presence of various lithium salts.

Figure 6 VFT plots for poly(organoboron halide)-imidazole complexes. 

Table 2 VFT Parameters for Poly(organoboron halide)-imidazole Complexes...

A synthesis of comblike organoboron polymer/boron stabilized imidoanion hybrids was examined via reactions of poly(organoboron halides) with 1-hexylamine and oligo(ethylene oxide) monomethyl ether and subsequent neutralization with lithium hydride (scheme 8). The obtained polymers (10) were amorphous soft solids soluble in common organic solvents such as methanol, THF, and chloroform. In the nB-NMR spectra (Fig. 11), neutralization of the iminoborane unit with lithium hydride... 

Zapf, A. Coupling of Aryl and Alkyl Halides With Organoboron Reagents (Suzuki Reaction). In Transition Metals for Organic Synthesis (2nd edn), Beller, M. Bolm, C. eds., 2004, 1, 211-229. Wiley-VCH Weinheim, Germany. (Review). 

We note that while tin reagents have often been employed for the organoboron halides/ the use of organostannanes as starting materials can also be applied to the synthesis of heavier group 13 derivatives. In the context of polyfunc-tional Lewis acid chemistry, this type of reaction has been employed for the preparation of ort/ o-phenylene aluminum derivatives. Thus, the reaction of 1,2-bis(trimethylstannyl)benzene 7 with dimethylaluminum chloride, methylaluminum dichloride or aluminum trichloride affords l,2-bis(dimethylaluminum)phenylene 37, l,2-bis(chloro(methyl)aluminum)phenylene 38 and 1,2-bis(dichloroalumi-num)phenylene 39, respectively (Scheme 16). Unfortunately, these compounds could not be crystallized and their identities have been inferred from NMR data only. In the case of 39, the aluminum derivative could not be separated from trimethyltin chloride with which it reportedly forms a polymeric ion pair consisting of trimethylstannyl cations and bis(trichloroaluminate) anions 40. 

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... 

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