Circumstantial evidence is presented which suggests that both side-on and end-on complexes are formed in the reactions of aliphatic, unbranched isonitriles RNC (R = C2H5-n-C6H13) with Fe+ in the gas phase. Depending on the chain length of the alkyl groups, two distinct processes are observed for either complexes upon collisional activation. One corresponds to oxidative addition of CH/CC bonds in the vicinity of the functional group to eventually cleave the R-NC bond (R = alkyl). This reaction, which is not observed for isomeric RCN/Fe+ complexes, dominates for R = C2H5-C4H9 and is caused by a side-on complexation of the RNC triple bond. For isonitriles with R = C5H11 and C6H13, this process is still operative; the major reaction, however, corresponds to H2 loss which is shown to involve functionalization of remote CH bonds, as has been demonstrated earlier for RCN/M+ complexes (M = Fe, Co, Ni). The experimental data further suggest that the binding energy of side-on complexes is larger for RNC/Fe+ than for RCN/Fe+. Metal ion induced isomerization of the type RNC → RCN does not seem to occur in the gas phase.
|Original language||English (US)|
|Number of pages||4|
|Journal||Journal of the American Chemical Society|
|State||Published - 1988|
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