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Reactions of Group 8, 9, and 10 Monocations (Fe + , Co + , Ni + , Ru + , Rh + , Pd + , Os + , Ir + , Pt + ) with Phosphane in the Gas Phase
Author(s) -
Mazurek Ulf,
Schwarz Helmut
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020503)8:9<2057::aid-chem2057>3.0.co;2-x
Subject(s) - chemistry , adduct , dehydrogenation , dissociation (chemistry) , medicinal chemistry , palladium , fourier transform ion cyclotron resonance , metal , bond dissociation energy , photochemistry , catalysis , ion , organic chemistry
The reactions of Group 8, 9 and 10 monocations with phosphane were studied under single‐collision conditions in a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer. Fe + is completely unreactive, Co + reacts slowly and shows both adduct formation and P−H bond activation, and Ni + reacts slowly as well but shows adduct formation only. In contrast to their first‐row congeners, the investigated second‐ and third‐row transition metal monocations show facile P−H bond activations. Remarkably, extensive dehydrogenations of the collision complexes yield cations MPH + , MP 2 + , MP 3 H + , MP 4 + and so on. Exceptional behaviour is shown by the two d 9 cations palladium (whose “dehydrogenation power” is rather limited) and platinum (which gives rise to a great manifold of only partially dehydrogenated species as well). Collision‐induced dissociation experiments suggest that P 2 and PH units are formed as ligands.