Abstract
The rates of C-H bond activation for various alkanes by [(N-N)Pt(Me)(TFE-d3)]+ (N-N = Ar-N=C(Me)-C(Me)=N-Ar; Ar = 3,5-di-tert-butylphenyl; TFE-d3 = CF3CD2OD) were studied. Both linear and cyclic alkanes give the corresponding alkene-hydride cation [(N-N)Pt(H)(alkene)]+ via (i) rate determining alkane coordination to form a C-H σ complex, (ii) oxidative cleavage of the coordinated C-H bond to give a platinum(IV) alkyl-methyl-hydride intermediate, (iii) reductive coupling to generate a methane σ complex, (iV) dissociation of methane, and (v) β-H elimination to form the observed product. Second-order rate constants for cycloalkane activation (C nH2n), are proportional to the size of the ring (k ∼ n). For cyclohexane, the deuterium kinetic isotope effect (kH/k D) of 1.28 (5) is consistent with the proposed rate determining alkane coordination to form a C-H σ complex. Statistical scrambling of the five hydrogens of the Pt-methyl and the coordinated methylene unit, via rapid, reversible steps ii and iii and interchange of geminal C-H bonds of the methane and cyclohexane C-H σ adducts, is observed before loss of methane.
Original language | English (US) |
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Pages (from-to) | 6915-6920 |
Number of pages | 6 |
Journal | Proceedings of the National Academy of Sciences of the United States of America |
Volume | 104 |
Issue number | 17 |
DOIs | |
State | Published - Apr 24 2007 |
Externally published | Yes |
Keywords
- Alkane functionalization
- C-H activation
- Catalysis
- Organometallic chemistry
ASJC Scopus subject areas
- General