Abstract
The cluster ion Me12 Fe8- is an unprecedented representative of organoiron species, which are of great interest because of their possible role as intermediates in iron-catalyzed cross-coupling reactions. To learn more about its behavior in solution, the possible formation of related cluster ions, and their reactivity, electrospray-ionization mass spectrometry and gas-phase experiments were performed. Me12 Fe8- adopts a highly dynamic behavior in solution and disappears in the presence of the chelating ligand N,N,N',N'-tetramethylethylenediamine. Besides homoleptic Me12 Fe8- , its heteroleptic analogues Me12-n Fe8 Phn- , n=1-5, are also accessible. Me12 Fe8- undergoes iron-halogen exchange reactions with aryl halides. These substrates, as well as their alkyl counterparts, mediate the formation of new homoleptic cluster ions up to Me18 Fe12- . In contrast, no evidence was found for oxidative additions or related reactions. Gas-phase fragmentation of the cluster ions results in numerous different reactions, ranging from the loss of single methyl radicals to the reductive elimination of MePh.
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