Transition metals cycloalkane reactions

Like protons, transition-metal ions are strongly acidic and they can, in principle, add to both the C—H and C—C bonds of alkanes. As already noted in the section on proton affinities (Table 1) strained cycloalkanes are intrinsically more basic than open-chain alkanes, and the reaction of cyclopropane with Pt((II) to form a platinacyclo-butane (equation 14) was the first reaction of a formally saturated hydrocarbon with a transition-metal ion . The driving force in this reaction is relief of the strain associated with the small ring. The resulting metallacyclobutane is essentially free of ring strain. Many low-valent transition-metal complexes have been found to react with cycloalkanes. Metal ions convet the strained hydrocarbons quadricyclane , cubane , bicyclo-[2.1.0]pentanes , bicyclo[3.1.0]hexanes , bicyclo[4.1.0]heptanes and bicyclo-butanes into less strained isomers (usually cyclohexanes). 

For instance, peroxodisulfate oxidizes metiiane to alcohols in the absenee of a metal at 105-115°C. Metal complexes ean be used as mediators for such reactions which permits carrying out the reactions at lower reaction temperatures. - In the ease of cycloalkanes, strongly electrophilic and oxidizing transition-metal ions play an irreplaceable role in the initiation step. 

Li and Kami demonstrated a DTBP-promoted CDC reaction between pyridine-iV-oxide and cycloalkanes in the absence of any transition metals (Scheme 8.24). Unactivated sp -hybridized C-H bonds on cycloalkanes, norbornane, and 1,4-dioxane can also undergo this reaction, giving the... 

---