Catalytic Oxy‐Functionalization of Methane and Other Hydrocarbons: Fundamental Advancements and New Strategies

Abstract

The controlled conversion of methane to methanol requires CH bond cleavage and CO bond formation. A catalytic cycle incorporating 1,2‐CH‐addition and net oxygen insertion with late transition metals has been proposed for this conversion. This Minireview discusses the current state of the art for each step of the proposed catalytic cycle.

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

“…In the context of this chapter, CH activation involves the reaction of a metal-ligand complex (MX) with an alkane CH bond to give an organometallic metal-alkyl (MR) intermediate that is hopefully more susceptible to substitution at carbon than the starting CH bond (Scheme 1) [17][18][19][20]. Generally, this CH bond functionalization strategy couples CH activation with a MR functionalization reaction where the organometallic intermediate is transformed into a partially oxidized alkane product.…”

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

“…This review is devoted to functionalization of carbon-hydrogen bonds [1][2][3][4][5][6][7][8][9][10][11][12][13] in various organic compounds, which is a very important process both from academic and practical point of view. Replacing hydrogen atoms in carbon-hydrogen compounds by functional groups X leads to valuable functionalized C-X compounds (Scheme 1a).…”

PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

“…However, examples of welldefined oxy-functionalizations of metal-hydrocarbyl complexes remain a challenge. [2,3,[8][9][10] Among several possible routes for the oxy-functionalization of M-R bonds (Scheme 1), one strategy that has not been extensively pursued is a process that involves a selective C-O bond formation by the reaction of oxygen-atom-transfer reagents (YO) with late-transition-metal complexes that possess M-R bonds (R = alkyl) (reactions II and III in Scheme 1). Examples of reactions of early-transition-metal-hydrocarbyl complexes that result in C-O bond formation with dioxygen or hydrogen peroxide are known, [11][12][13][14][15][16][17][18][19] and the extension of net dioxygen insertion into late-transition-metalhydride or -alkyl bonds has been reported recently.…”