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Cobalt porphyrins were found to catalyze the transfer hydrogenation of the carbon−carbon σ bond of [2.2]paracyclophane (PCP) with the solvent DMF serving as the hydrogenating agent. Successful trapping experiments with benzene solvent and the kinetic isotope effect (4.9) suggested the presence of benzyl radical intermediates in undergoing hydrogen atom transfer from DMF as the rate-limiting step. The rate law was established by initial rate measurements to be rate = k obs [Co II (ttp)]- [PCP].C atalytic carbon−carbon bond activation (CCCA) is the key chemical transformation in hydrocracking, turning crude oil into petroleum. 1 CCCA holds the potential to convert heavy polymeric residues and biomass into lighter, economically valuable chemicals. 2 Despite the usefulness of CCCA, examples with transition-metal complexes in homogeneous media remain limited. 3 The small number of literature reports on CCCA reflects the inertness of the C−C σ bond relative to the C−H bond. 4 CCCA with transition-metal complexes in homogeneous media mainly employs strategies such as chelation assistance, 5 ring strain relief, 6 and carbonyl functionality 7 to generate organometallic intermediates, followed by subsequent rearrangement of the carbon skeleton 8 or M−C σ-bond hydrogenation with H 2 9 to complete the catalytic cycle. Our group has been interested in carbon−carbon bond activation (CCA) of organic substrates and has reported several stoichiometric examples. 10 Recently, we have developed rhodium and iridium metalloporphyrin (M(por), M = Rh, Ir) catalyzed C−C σ-bond hydrogenation of [2.2]paracyclophane (1) with water as the hydrogenating agent. 11 In light of these successes, we wish to extend the catalysis to a much less reactive but more easily accessible and cheaper cobalt porphyrin catalyst. Co(II) porphyrin is expected to have a lower reactivity than the corresponding rhodium and iridium porphyrin analogues since (1) Co−C bonds are generally weaker 12 and (2) Co II (por) metalloporphyrin radical has a lower SOMO energy level. 13 As a result of low reactivity, CCA by cobalt complexes remains scarce in the literature. 14
Cobalt porphyrins were found to catalyze the transfer hydrogenation of the carbon−carbon σ bond of [2.2]paracyclophane (PCP) with the solvent DMF serving as the hydrogenating agent. Successful trapping experiments with benzene solvent and the kinetic isotope effect (4.9) suggested the presence of benzyl radical intermediates in undergoing hydrogen atom transfer from DMF as the rate-limiting step. The rate law was established by initial rate measurements to be rate = k obs [Co II (ttp)]- [PCP].C atalytic carbon−carbon bond activation (CCCA) is the key chemical transformation in hydrocracking, turning crude oil into petroleum. 1 CCCA holds the potential to convert heavy polymeric residues and biomass into lighter, economically valuable chemicals. 2 Despite the usefulness of CCCA, examples with transition-metal complexes in homogeneous media remain limited. 3 The small number of literature reports on CCCA reflects the inertness of the C−C σ bond relative to the C−H bond. 4 CCCA with transition-metal complexes in homogeneous media mainly employs strategies such as chelation assistance, 5 ring strain relief, 6 and carbonyl functionality 7 to generate organometallic intermediates, followed by subsequent rearrangement of the carbon skeleton 8 or M−C σ-bond hydrogenation with H 2 9 to complete the catalytic cycle. Our group has been interested in carbon−carbon bond activation (CCA) of organic substrates and has reported several stoichiometric examples. 10 Recently, we have developed rhodium and iridium metalloporphyrin (M(por), M = Rh, Ir) catalyzed C−C σ-bond hydrogenation of [2.2]paracyclophane (1) with water as the hydrogenating agent. 11 In light of these successes, we wish to extend the catalysis to a much less reactive but more easily accessible and cheaper cobalt porphyrin catalyst. Co(II) porphyrin is expected to have a lower reactivity than the corresponding rhodium and iridium porphyrin analogues since (1) Co−C bonds are generally weaker 12 and (2) Co II (por) metalloporphyrin radical has a lower SOMO energy level. 13 As a result of low reactivity, CCA by cobalt complexes remains scarce in the literature. 14
Bio-oil has been identified as a major feedstock for the production of renewable fuels. As bio-oil has a high O-content, and therefore a low heating value and low stability over time, upgrading is desirable to remove the oxygen and to make it similar to crude oil. Here, we examine the two general catalytic routes for bio-oil upgrading: cracking and hydrodeoxygenation (HDO). Zeolite cracking is an alternative path in which acid zeolites are used as catalysts for the deoxygenation reaction. In these systems, hydrogen is not required, and so the operation is performed at atmospheric pressure. However, HDO is usually conducted under high H2 pressure in order to remove the O-containing compounds and hence to produce a high grade oil product. The catalysts employed for HDO are traditional hydrodesulfurization (HDS) catalysts, such as Co–MoS2/Al2O3, or metal catalysts. However, the life of the catalyst (more than 200 h on stream) has not been demonstrated. Of the two catalytic routes mentioned above, HDO appears to have the best potential, as zeolite cracking cannot produce fuels of an acceptable grade. Although HDO is considered the best option to produce transportation fuels of a grade and cost equivalent to present fossil fuels, several problems still have to be solved. An understanding of the carbon forming mechanisms and kinetics, an evaluation of the requirement for high pressure, and sustainable sources of hydrogen are some of the areas that have to be elucidated before the process can be commercialized.
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