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Title: Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.
Authors:
; ; ; ;
Publication Date:
OSTI Identifier:
970051
Report Number(s):
LBNL-1351E
TRN: US201007%%389
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: The Journal of Physical Chemistry A; Journal Volume: 112; Journal Issue: 49; Related Information: Journal Publication Date: December 11, 2008
Research Org:
Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
Sponsoring Org:
Chemical Sciences Division
Country of Publication:
United States
Language:
English
Subject:
37; ADDUCTS; AFFINITY; ALKANES; ALKENES; CATIONS; CONFIGURATION; ELECTRONS; ETHANE; HYDROCARBONS; HYDROGEN; ION CYCLOTRON-RESONANCE; MASS SPECTROSCOPY; METHANE; PROPANE; PROPYLENE; RARE EARTHS lanthanides, mass spectrometry, gas-phase reactivity, organometallics