Methane functionalization

Brian L Conley, William J. Tenn, III, Kenneth J. H. Young, Somesh Canesh, Steve Meier, Vadim Ziatdinov, Oleg Mironov, Jonas Oxgaard, Jason Conzales, William A. Goddard, III, and Roy A. Periana 

Activation of Small Molecules. Edited by William B. Tolman Copyright 2006 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 3-527-31312-5 

I SO Trillion to 00 TriHon Cubic Feet 110 Trillion to 40 Trillion Cubic Feet 

II Trillion to 0 Trillion Cubic Feet (3 1 Trillion Cubic Feet 

petroleum is our primary hydrocarbon feedstock. It is estimated [1] that at the beginning of 2004, worldwide reserves were 1.27 trihion barrels of oil. At current usage this supply is projected to last -50 years. The other important hydrocarbon feedstocks are coal and natural gas. Methane, CH4, is the major component of natural gas (75-90%) and as shown in Fig. 7.2, is one of the most abundant hydrocarbons on the planet and is widely distributed. Current estimates are that natural gas reserves (6,100 trillion cubic feet) are comparable to oil on an energy content basis. If the estimates of natural gas in methane hydrate deposits in the deep oceans are considered, the amount of methane on the planet could far exceed the known oil reserves Given the abundance, wide distribution, hi er hydrogen to carbon ratio and low sulfur content compared to oil and coal, methane could become the hydrocarbon feedstock of choice that could lead to a Methane Economy for the next several decades. 

---

Fig. 4 Resonant frequency changes with time due to repetitive FIA melamine injections, for the MIP-QCM chemosensor. Melamine concentration is indicated with number at each curve. Inset shows FIA calibration plots for (1) melamine and its interfering compounds, such as (2) ammeline, (3) cyanuric acid, and (4) cyromazine. Volume of the injected sample solution was 100 pL. The flow rate of the 1 mM FIC1 carrier solution was 35 pL min-1. The MIP film was prepared by electropolymerization of 0.3 mM bis(2,2 -bithienyl)-benzo-[18-crown-6]methane functional monomer and 0.3 mM 3,3 -bis[2,2 -bis(2,2 -bithiophene-5-yl)]thianaphthene cross-linking monomer, in the presence of 0.1 mM melamine, in the trihexyl(tetradecyl)phosphonium tris(pentafluor-oethy 1)-trifluorophosphate ionic liquid ACN (1 1 v/v) solution, which was 0.9 mM in trifluoroacetic acid (pH = 3.0). The melamine template was extracted from the MIP film with 0.01 M NaOH before the determinations (adapted from [134])...

The Shilov Pt(II) system for methane functionalization has been studied using computations. For example, using MCl2(H20)2 (M = Pt or Pd) systems as models for Shilov-type reactions, the overall catalytic cycle was studied using a combination of... 

The relatively constant product heating value, in spite of the changes in the potassium content, is indicative of the nickel catalyst s methanating function. This agrees with previously presented results. On the other... 

These electron-deficient porphyrins and their metal complexes have proven to be valuable tools to study many aspects of porphyrin structure and function. An in-depth discussion of this area is beyond the scope of this review but examples will be cited. Thus, large substituent-dependent variations in electron-transfer properties of cobalt complexes were ascribed to widely varying inner sphere reorganization energies related to core expansion and contraction. In another example, a ruthenium complex functioned as a potential methane functionalization catalyst by virtue of the ability of... 

Reductive ehmination of methanol, the last step in a hypothetical methane functionalization scheme, can be observed from the monomethyl-Pt(lV) species, but only at elevated temperature mechanistic studies indicate that the formation of methanol is preceded by isomerization, as shown in Scheme 29 [73]. This finding is in accord with earher studies on C-X bond formation, which require dissociation of a ligand trans to the alkyl group before nucleophilic attack at C in the five-coordinate intermediate. The original oxidation product has a pyridine ligand trans to... 

Nelson AP, DiMagno SG (2000) Umpolung of a metal-carbon bond a potential route to porphyrin-based methane functionalization catalysts. J Am Chem Soc 122(35) 8569-8570... 

Requirements of Methane Functionalization Chemistry Influenced by Plant Design... 

CH Activation as a Pathivay to Economical Methane Functionalization via CH Eh/droxylation 245... 

CH Activation as a Pathway to Economicai Methane Functionalization via CH Hydroxylation... 

---