There is a large motivation to convert natural gas to a more valuable feedstock for the chemical industry. Conversion of methane (and other alkanes) is not easy, due to a very inert C-H bond. In particular, methane has the strongest C-H bond amongst alkanes, which is the main obstacle in its conversion to other, more valuable organic molecules. Current technology uses high temperature methods to convert natural gas to synthesis gas, and therefore consumes large amounts of energy while producing mixtures of products that require further separation and purification. It has neen found that the titanium neopentylidyne complex ((PNP)Ti=CHtBu(CH2tBu)) can react at room temperature with methane and ethane.1,2 Use of this lighter, less expensive metal that does not need photochemical activation to start the reaction is extremely favorable. Experimental results from kinetic isotope effect studies shows that intermolecular C–H bond activation step of methane is not rate determining step, and that the rate determining step is the dissociation of CH3tBu and formation of structure A (See figure). We have studied computationally the proposed reaction mechanism for C–H bond activation for methane and present the results here. The calculated mechanism is in agreement with the experimental data, and shows that barrier for formation of precursor A is highest. [1] Flores J. A.; Cavaliere V. N.; Buck D.; Pinter B.; Chen G.; Crestani M. G.; Baik M-H.; Mindiola D. J; Chem. Sci., 2011, 2, 1457-1462. [2] Cavaliere V. N.; Crestani M. G.; Pinter B.; Pink M.; Chen C-H.; Baik M-H.; Mindiola D. J.; J. Am. Chem. Soc. 2011, 133, 10700–10703.

C-H activation by a titanium neopentylidyne complex

251st National Meeting (2016)

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