Abstract
The lithium and sodium ion complexes of the polyglycol-derived radicals (R•) HOCH2CH2O• (1•), H(OCH2CH2)2O• (2•), HOCH2CH2OCH2• (3•), H(OCH2CH2)2OCH2• (4•), HOCH2CH2OCH2CH2• (5•), and H(OCH2CH2)2OCH2CH2• (6•) are produced in the gas phase by fast atom bombardment ionization and their structures and unimolecular chemistry are investigated by tandem mass spectrometry. Parallel ab initio MO calculations show that the [R• + X]+ (X = Li, Na) complexes carry their positive charge and unpaired electron at distinct centers, thus representing a novel type of distonic radical cations. Radical reactions prevail for all [R• + X]+ species studied. The predominant dissociation of metalated 1•−4• (−O• or −OCH2• terminus) involves cleavage of CH2O via ion−molecule complexes in which the newly detached formaldehyde molecule remains bound to the metal ion. With Li+ cationization, H• transfer within these intermediate complexes also takes place, leading to the elimination of OCH•; this reaction is particularly competitive a...
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