Diborane determination

Table 3-11 gives the initial rate data [-d(B2Hg)/dt] reported for the gas phase reaetion of diborane and aeetone at 114°C BjHg -i-dMejCO —> 2(Me2CHO)2BH. If a rate expression is of the form Rate = PmcjCO determine n, m, and k. 

On the other hand, the observed syn preference of 59a is consistent with a study of hydroboration of 59a with diborane by Schueler and Rhodes [127], who obtained a mixture of the monoalcohols (symanti = 74 26) upon oxidative work-up. A similar magnitude of. yyn-preference was found (syn anti = 73 27) in the hydroboration with a bulkier borane, 2,3-dimethyl-2-butylborane (thexyl borane) [127]. This lack of effect of the bulk of the reagent in the hydroboration of 59a is consistent with the idea that the n face of 59a is free from steric bias [127], and that the syn preference of 59a found in dihydroxylation and epoxidation is non-sterically determined [128]. 

Diborane is used in silicon chip manufacture. One facility uses a 500-lb bottle. If the entire bottle is released continuously during a 20-min period, determine the location of the 5 mg/m3 ground-level isopleth. It is a clear, sunny day with a 5 mph wind. Assume that the release is at ground level. 

Reconsider Problem 5-10. Assume now that the bottle ruptures and that the entire contents of diborane are released instantaneously. Determine, at 15 min after the release,... 

At about the same time, the pyrolysis of diborane was studied by Bragg et al.88 in the temperature range 90-130 °C. These workers again used a static system (reaction vessel volume 212 cm3) and followed the conversion both by measurement of pressure increase and by determination of the amount of hydrogen formed. The system was also examined by mass spectrometric analysis. The empirical rate law was found to be... 

Two carborane cations, zV/ -2,3,4,5,6-McsC5BBr+ and the tentatively proposed arachno-N ci WX I71, were reported. The identity and pyramidal structure of the pentacarbaborane cation was determined by X-ray crystallography.112 The small arachno-carborane was detected on the basis of ab initio computations and 11B NMR data in the mixture from reaction of the 2-propyl cation with diborane.113 Two neutral adducts based on the pentacarbaborane cation, ///V/9-2,3,4,5,6-McsCsBBKCI2 (R = Cl or SiClj), were made from MesCsSiMe3 or (MesCs Si with B2CI4, respectively.114 The BCI3 adduct was structurally characterized by X-ray crystallography. 

It was shown that the rate of decomposition of diborane follows a rate law that corresponds to d(B2H6) = k B2H(, 2. This is consistent with the dissociation of diborane into BH3 as the rate determining step with formation of B3H9. This intermediate then decomposes with hydrogen evolution to give unstable B3H7 which on reaction with further BH3 produces B4H10 as the first isolable poly-borane ... 

Bis(dichloroboryl)benzene (6) is an important starting material which lends itself to facile derivatization. As shown by Piers, it cleanly reacts with bis(penta-fluorophenyl)zinc to afford the corresponding bidentate Lewis acid 13 (Scheme 7) The molecular structure of diborane 13 has been determined and is shown in Fig. 1. In this structure, the vicinal boron atoms are held at 3.26 A and from one another and seem to be ideally positioned to cooperatively interact with monoatomic anions. The fully fluorinated version of this bidentate Lewis acid has also been prepared. Original efforts focused on the use of 1,2-bis(dichloroboryl)tetrafluorobenzene 14 as a starting material (Scheme 8). This compound could be observed in the early stage of the reaction of trimeric perfluoro-o-phenylenemercury (4) with boron trichloride, but was found to be unstable toward condensation into 9,10-dichloro-9,10-dihydro-9,10-diboraoctafluoroanthracene 15. The successful synthesis of the fully fluorinated... 

In an effort to prepare bidentate boranes as colorimetric anion sensors, the incorporation of chromophoric boron moieties has also received attention. Reaction of lO-bromo-9-thia-lO-boranthracene 33 with dimesityl-1,8-naphthalenediylborate 26 affords diborane 34 (Scheme 14). This bright yellow diborane is soluble in chloroform, THF and pyridine. It has been fully characterized but its X-ray crystal structure could not be determined experimentally. Its structure was computationally optimized using DFT methods (B3LYP, 6-31 + G for the boron and sulfur... 

Symmetry restrictions may also be placed on the active orbitals in order to determine the nature of the resulting modern valence bond solution. This is exemplified by the common use of o - n separation for planar molecules (c/ Section 5). In earlier applications to ozone and diborane [2,4] it was also seen that the distribution of active orbitals among the irreducible representations was the deciding factor for the types of VB solution possible. It should also be borne in mind here that the nature of the lowest-lying CASSCF solution may not always coincide with that of the optimal fully-variational modem VB wavefunction. 

Diamond (1966) has applied a filtering procedure in the refinement of protein structures, in which poorly determined linear combinations are not varied. In charge density analysis, the principal component analysis has been tested in a refinement of theoretical structure factors on diborane, B2H6, with a formalism including both one-center and two-center overlap terms (Jones et al. 1972). Not unexpectedly, it was found that the sum of the populations of the 2s and spherically averaged 2p shells on the boron atoms constitutes a well-determined eigenparameter, while the difference is very poorly determined. Correlation between one- and two-center terms was also evident in the analysis. 

The ESR spectra of a series of triarylboron anion radicals have been determined and show selective line-broadening effects (95). The radical anions of diborane, generated in an argon matrix at 77 K by irradiation with a-rays have been studied by ESR (121). The vanadium-aluminum complex obtained on mixing dichlorobis(7r-cyclopentadienyl)vanadium with ethylaluminum dichloride, a system that catalyzes the polymerization of ethylene to give a polymer with good characteristics, has been characterized by ESR and ultraviolet studies (44). 

The order of reactivities of various functional groups determined under standard conditions (using externally generated diborane, and tetrahydrofuran as solvent) is acid > alkene > ketone > nitrile > epoxide > ester > acid chloride.33 Acids, aldehydes, ketones, epoxides, nitriles, lactones and azo compounds are reduced rapidly, esters more slowly and chloral, acid chlorides and nitro compounds are inert. Double bonds undergo the hydroboration reaction,25 nitriles and azo compounds are reduced to amines, and the remaining groups to alcohols. Ketones can be reduced selectively in the presence of epoxides. Contrary to the order of reactivities given above, it has been claimed that nitriles are reduced more rapidly than ketones.223... 

The fact that HB02, a reactive compound, was produced rather than the relatively inert B203 was a factor in the discontinuation of the investigation of diborane as a fuel, (a) What mass of liquid oxygen (LOX) would be needed to burn 50.0 g of B2H6 (b) Determine the mass of HB02 produced from the combustion of... 

Approximate equilibrium constants for the gas-phase reaction at 300° T have been determined for the trimethylborane-diborane exchange from equilibrium experiments and from thermodynamic data (164,261) with the computed constants listed in parentheses in Eqs. (68)-(71). 

Multiply the concentration of boron as determined in the analysis by the stoichiometric factor 1.28 to calculate the concentration of diborane. 

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