185850-67-3Relevant academic research and scientific papers
Intramolecular and intermolecular C-H activation at a cationic PtII center
Holtcamp, Matthew W.,Henling, Lawrence M.,Day, Michael W.,Labinger, Jay A.,Bercaw, John E.
, p. 467 - 478 (2008/10/08)
Syntheses and C-H bond activation reactions of the novel electrophilic PtIIcomplexes [(tmeda)Pt(CH3)(OEt2)][BArf], [(tmeda)Pt(CH3)(THF)][BArf], and [(tmeda)Pt(CH3)(NC5F5)][BArf] are described {[BArf]- = [(3,5-C6H3(CF3)2)4B] -} (tmeda is N,N,N′ ,N′-tetramethylethylenediamine). [(tmeda)Pt(CH3)(OEt2)][BArf] and [(tmeda)Pt(CH3)(THF)][BArf] are unstable at room temperature, yielding methane and the Fischer carbene PtII hydrides, [(tmeda)Pt(=C(CH3)(OCH2CH3))(H)][BAr f] and [(tmeda)Pt(=CCH2CH2CH2O)(H)][BArf]. The methane liberated from [(tmeda)Pt(CH3)(OEt2-d10)][BArf] consists of an isotopomeric mixture, (CH4, CH3D, CH2D2, and CHD3), indicating a multiple H/D exchange reaction following the C-D activation and prior to methane loss. [(tmeda)Pt(CH3)(THF-d8)][BAr] liberates CH4 and CH3D. Methane-13C, cyclohexane, toluene, and benzene react with [(tmeda)Pt(CH3)(NC5F5)][BArf] to yield methane and new organoplatinum complexes. Deuterated alkanes and arenes react with [(tmeda)Pt(CH3)(NC5F5)][BArf] to give a mixture of methane isotopomers. The relevance of these results to the oxidation of alkanes by aqueous platinum complexes is discussed.
