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Electron ionization‐induced fragmentation of diphenylphosphino‐ and diphenylphosphinoyl‐substituted ferrocene derivatives
Author(s) -
Polášek Miroslav,
Štěpnička Petr
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(199808)33:8<739::aid-jms693>3.0.co;2-3
Subject(s) - chemistry , fragmentation (computing) , electron ionization , ferrocene , mass spectrum , molecule , ion , phosphine , medicinal chemistry , phosphine oxide , metal , stereochemistry , crystallography , ionization , organic chemistry , catalysis , electrode , computer science , electrochemistry , operating system
Electron ionization mass spectra of several diphenylphosphino‐ and diphenylphosphinoyl‐substituted ferrocenes of the general formula [(η 5 ‐C 5 H 4 X)Fe(η 5 ‐C 5 H 4 Y)], [X/Y=PPh 2 /H (1), P(O)Ph 2 /H (2), PPh 2 /CO 2 H (3), P(O)Ph 2 /CO 2 H (4), PPh 2 /CO 2 CH 3 (5) and P(O)Ph 2 /CO 2 CH 3 (6)] and of their deuterated analogues [X/Y=PPh 2 /CO 2 D (3a), PPh 2 /CO 2 CD 3 (5a)] are reported. Fragmentation pathways for all compounds studied are 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 confirmed. 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 different 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 different behaviour when originating from fragmentation of different parent molecules. © 1998 John Wiley & Sons, Ltd.