Investigation of thetrans effect in the fragmentation of dinuclear platinum complexes by electrospray ionization surface-induced dissociation tandem mass spectrometry

✍ Scribed by Schaaff, Thomas G.; Qu, Yun; Farrell, Nicholas; Wysocki, Vicki H.

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 346 KB
• Volume: 33
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/(sici)1096-9888(199805)33:5<436::aid-jms649>3.0.co;2-k

✦ Synopsis

Cis and trans isomers of two dinuclear platinum complexes, cis-¿Pt(NH3)2Cl¿2 mu-(NH2(CH2)nNH2)2 (1,1/c,c) and trans-¿Pt(NH3)2Cl¿2 mu-(NH2(CH2)nNH2)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.