Adduct ion formation by metal complexes under methane negative chemical ionization conditions

✍ Scribed by G. W. Dillow; I. K. Gregor; M. Guilhaus

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 623 KB
• Volume: 21
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210210309

✦ Synopsis

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(I1) and copper(n) in the presence of O,, OzN2 and N4 donor atom sets are characterized by two dominant series of adduct ions of the form [M+C,H,,]-and [M + CnHk+J at m / z values above the molecular ion, [MI-. Insertion of the 'CH radical into the ligand followed by radicallradical recombination and electron capture is proposed as the major mechanism leading to the formation of [M + C,H,]-adduct ions. A second pathway involves ligand substitution by 'C,H,+, 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 + CnHk+J-adduct ions.