title: Theoretical Investigation of the Methanol Decomposition by Fe+)and Fe(C2H4)+: A π-Type Ligand Effect.
abstract: Density functional theory has been used to probe the mechanism of gas-phase methanol decomposition by bare Fe(+) and ligated Fe(C(2)H(4))(+) in both quartet and sextet states. For the Fe(+)/methanol system, Fe(+) could directly attach to the O and methyl-H atoms of methanol, respectively, forming two encounter isomers. The methanol reaction with Fe(+) prefers initial C-O bond activation to yield methyl with slight endothermicity, whereas CH(4) elimination is hindered by the strong endothermicity and high-energy barrier of hydroxyl-H shift. For the Fe(C(2)H(4))(+)/methanol system, the major product of H(2)O is formed through six elementary steps: encounter complexation, C-O bond activation, C-C coupling, β-H shift, hydride H shift, and nonreactive dissociation. Both ligand exchange and initial C-O bond activation mechanisms could account for ethylene elimination with the ion products Fe(CH(3)OH)(+) and (CH(3))Fe(OH)(+), respectively. With the assistance of a π-type C(2)H(4) ligand, the metal center in the Fe(C(2)H(4))(+)/CH(3)OH system avoids formation of unfavorable multi-σ-type bonding and thus greatly enhances the reactivity compared to that of bare Fe(+).
authors.forename: Hongguang
authors.initials: H
authors.lastname: Sui
authors.forename: Fengyun
authors.initials: F
authors.lastname: Zhang
authors.affiliation: Department of Pharmacy, Affiliated Hospital of Qingdao University , Qingdao, Shandong 266003, People's Republic of China.
authors.forename: Fei
authors.initials: F
authors.lastname: Hou
authors.forename: Lianming
authors.initials: L
authors.lastname: Zhao
authors.forename: Wenyue
authors.initials: W
authors.lastname: Guo
authors.forename: Jun
authors.initials: J
authors.lastname: Yao
mesh_terms: D005030:Ethylenes / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D005030:Ethylenes; D008024:Ligands; C036216:ethylene; D007501:Iron; D000432:Methanol