Experimental evidence is presented that RCN/M+ complexes (M = Co, Ni) exhibit practically identical reactivities upon collisional activation in the gas phase, while the analogous RCN/Fe+ systems are distinct. Insertion of the (complexed) transition metal ion M+ into internal CH bonds of linear alkyl nitriles commences for the RCN/Fe+ system with C(8) while, for the RCN/Co+ and RCN/Ni+ species, a trajectory is operative by which insertion occurs already at C(7). This behaviour can be explained by the different bonding situation of the RCN/Fe+ versus RCN/M+ (M = Co, Ni) systems. In the former, the deviation from the linear C-C-N-Fe+ alignment is less pronounced than in the C-C-N-M+ system (M = Co, Ni) with the consequence that CH bonds of the methylene chain closer to the functional group add oxidatively to the metal ion for M = Co, Ni. Some analogies with the recently described metal-silylene system are discussed.
|Original language||English (US)|
|Number of pages||8|
|Journal||International Journal of Mass Spectrometry and Ion Processes|
|State||Published - Nov 25 1987|
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