Iminoboranes oligomerization

Equation (25) may shed light on the general path of the iminoborane oligomerization. I propose the formation of cyclodimers to be the first stage of such oligomerizations. If a cyclodimer is stable to an excess of iminoborane, it will be isolated (Table III). Otherwise the cyclodimer is attacked by the excess iminoborane according to Eq. (25), and the borazine is formed via the Dewar borazine. In special cases, the Dewar borazine will be the final product. The first step determines the rate of such a sequence of reactions. If the cyclodimerization step becomes relatively fast, so that the first and the second step are comparable in rate, both the cyclodimer and the cyclotrimer will be found this is true for the thermal stabilization of sBuBNsBu. Catalysts for the cyclodimerization make the first step more rapid than the second one. 

Synthesis. Iminoboranes, thermodynamically unstable with respect to oligomerization can be isolated under laboratory conditions by making the oligomerization kineticaHy unfavorable. This is faciUtated by bulky substituents, high dilution, and low temperatures. The vacuum gas-phase pyrolysis of (trimethylsilylarnino)(aLkyl)haloboranes has been utilized as an effective method of generating iminoboranes RB=NR as shown in equation 19 for X = F,... 

The chemistry of these compounds reflects the unsaturated nature of the B—N triple bond. Polar compounds add to iminoboranes, provided the addition proceeds more rapidly than oligomerization of R SIR ( ). For example, for R = R = CH(CH3)2 or /-C H. ... 

A striking difference between alkynes and iminoboranes appears to be their kinetic stability. As was pointed out in Section II, iminoboranes are metastable, in general, at temperatures far below room temperature. Alkynes are also metastable, but their stabilization requires either high temperature or effective catalysts. We assume the polarity of the B—N bond to be a chief reason for these differences. This idea is supported by the observation that strongly polar alkynes (e.g., FC=CH, FC=CfBu) do oligomerize or polymerize at room temperature quite rapidly (25). Polar additions will generally be the predominant reaction for iminoboranes (Sections V,VI). 

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