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Investigation of the trans effect in the fragmentation of dinuclear platinum complexes by electrospray ionization surface‐induced dissociation tandem mass spectrometry
Author(s) -
Schaaff Thomas G.,
Qu Yun,
Farrell Nicholas,
Wysocki Vicki H.
Publication year - 1998
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199805)33:5<436::aid-jms649>3.0.co;2-k
Subject(s) - chemistry , fragmentation (computing) , electrospray ionization , tandem mass spectrometry , collision induced dissociation , dissociation (chemistry) , mass spectrometry , platinum , electrospray , tandem , protein mass spectrometry , extractive electrospray ionization , chromatography , organic chemistry , computer science , catalysis , operating system , materials science , composite material
Cis and trans isomers of two dinuclear platinum complexes, [ cis ‐{Pt(NH 3 ) 2 Cl} 2 μ‐(NH 2 (CH 2 ) n NH 2 )](NO 3 ) 2 (1,1/c,c) and [ trans ‐{Pt(NH 3 ) 2 Cl} 2 μ‐(NH 2 (CH 2 ) n NH 2 )](NO 3 ) 2 (1,1/t,t), where the diamine was 1,4‐butanediamine ( n =4) or 1,6‐hexanediamine ( n =6), were studied using electrospray ionization surface‐induced dissociation (ESI/SID) tandem mass spectrometry (MS/MS). The same fragment ions were observed for both the cis and trans isomers of each complex ( n =4 or 6), but the relative intensities were dependent on the isomer studied. The ESI/SID data and energy‐resolved mass spectra show that the position of the chloride plays a significant role in the fragmentation of these ions. Two major fragmentation pathways were detected for the complexes. The cleavage of the Pt−N bond trans to chloride was the most favorable pathway for both isomers of the complexes following the ion–surface collision. The differences in the ESI/SID spectra between the cis and trans isomers can be explained by the trans effect, namely that the Pt−N bond trans to chloride is the most labile bond. © John Wiley & Sons, Ltd.