Electron ionization-induced fragmentation of diphenylphosphino- and diphenylphosphinoyl-substituted ferrocene derivatives

✍ Scribed by Polášek, Miroslav; Štěpnička, Petr

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 335 KB
• Volume: 33
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/(sici)1096-9888(199808)33:8<739::aid-jms693>3.0.co;2-3

✦ Synopsis

Electron ionization mass spectra of several diphenylphosphino-and diphenylphosphinoyl-substituted ferrocenes of the general formula

(1), ( 2), (3),

(5) and ( 6) ] and of their deuterated analogues

) ] are reported. Fragmentation pathways for all compounds studied are PPh 2 /CO 2 D PPh 2 /CO 2 CD 3 presented. The proposed fragmentation schemes are based on accurate mass measurements, observations of metastable ion decompositions and the study of collisionally activated dissociations of important ions.

A key role of the ferrocenyl metal centre in the transfer of oxygen-containing groups was conÐrmed. However, the introduction of another oxophilic group, i.e. trivalent phosphorus of the diphenylphosphino group in the present case, leads to a competition between the two di †erent oxygen acceptors now present in the molecule. If the oxophilicity of the phosphorus atom is saturated by P-oxide formation, the fragmentation pathways change markedly in comparison with those of the parent phosphine. The structure of selected isobaric ions common to the spectra of various compounds is discussed as some of these exhibit di †erent behaviour when originating from fragmentation of di †erent parent molecules.