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Bimolecular Gas‐Phase Reactions of d‐Block Transition‐Metal Cations With Dimethyl Peroxide: Trends Across the Periodic Table
Author(s) -
Wesendrup Ralf,
Schalley Christoph A.,
Schröder Detlef,
Schwarz Helmut
Publication year - 1995
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/chem.19950010907
Subject(s) - peroxide , table (database) , gas phase , block (permutation group theory) , chemistry , transition metal , metal , inorganic chemistry , phase (matter) , organic chemistry , catalysis , mathematics , computer science , geometry , data mining
The bimolecular gas‐phase reactions of d‐block transition‐metal cations M + with dimethyl peroxide were screened by means of Fourier transform ion cyclotron resonance mass spectrometry. The rich chemistry can be classified into four types of reactions: i) Oxygen‐atom transfer to generate MO + , ii) elimination of radicals, mostly CH 3 O ˙ , iii) intramolecular redox reaction of dimethyl peroxide to form CH 3 OH, CH 2 O and CO, and iv) charge transfer from the metal cation to produce CH 3 OOCH 3 + . Some general trends became apparent from this study. For example, the “early” transition metals almost exclusively induce oxygen transfer to generate MO + , in line with the notoriously high oxophilicities of these metals, and electron transfer is only observed for Zn + and Hg + . Both the radical loss and the disproportionation reaction emerge from a rovibrationally highly excited insertion intermediate (CH 3 O) 2 M + , and for the first‐row metals the branching ratio of the competing processes seems to be affected by the M + OR bond strengths as well as the electronic groundstate configurations of M + . For the 4d and 5d cations Ru + Ag + and Pt + Au + , respectively, products resulting from intramolecular redox reactions dominate; this probably reflects the higher propensity of these metal ions to facilitate β‐hydrogen atom shifts.