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Adduct ion formation by metal complexes under methane negative chemical ionization conditions
Author(s) -
Dillow G. W.,
Gregor I. K.,
Guilhaus M.
Publication year - 1986
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210210309
Subject(s) - adduct , chemistry , radical , chemical ionization , electron ionization , ligand (biochemistry) , mass spectrometry , metal , mass spectrum , fast atom bombardment , ionization , ion , cobalt , photochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , biochemistry , receptor , chromatography
Negative chemical ionization mass spectrometry is used as a probe to examine reactions between hydrocarbon radicals and metal complexes in the gas phase. The methane negative chemical ionization mass spectra of 27 complexes of cobalt( II ), nickel( II ) and copper( II ) in the presence of O 4 , O 2 N 2 and N 4 donor atom sets are characterized by two dominant series of adduct ions of the form [M + C n H 2 n ] − and [M + C n H 2 n +1 ] − at m / z values above the molecular ion, [M] − . Insertion of the CH radical into the ligand followed by radical/radical recombination and electron capture is proposed as the major mechanism leading to the formation of [M + C n H 2 n ] − adduct ions. A second pathway involves ligand substitution by C n H 2 n +1 radicals concomitant with H elimination and electron capture. Oxidative addition at the metal followed by ionization is suggested as the principal pathway for the formation of [M + C n H 2 n +1 ] − adduct ions.