Journal
HELVETICA CHIMICA ACTA
Volume 91, Issue 10, Pages 1902-1915Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/hlca.200890204
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Funding
- Deutsche Forschungsgemeinschaft (DFG)
- Fonds der Chemischen Industrie
- Academy of Sciences of the Czech Republic [Z40550506]
- Cluster of Excellence
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Mechanistic details for the formation of methane from the title compound as well as the combined elimination of (CH3)(2)S/CH4 are derived from various mass-spectrometric experiments including deuterium-labeling Studies and DFT calculations. For the first process, i.e.. methane formation, we have identified three competing pathways in which the intact, Pt-bonded methyl group combines with a H-atom that originates from a phenyl substituent (ca. 7%), the dimethyl sulfide ligand (ca. 41%), and a methyl group of the diazabutadiene backbone (ca. 52%). In contrast. in the combined (CH3)(2)S/CH4 elimination. the methane is specifically formed from the Pt-bound CH3 group and a H-atom provided by one of the phenyl groups ('cyclometalation').
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