title: Sphalerite is a geochemical catalyst for carbon-hydrogen bond activation.
abstract: Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth's deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon-hydrogen bond in the dimethylcyclohexanes.
authors: Department of Chemistry and Biochemistry and.
authors: Jessie A
authors: JA
authors: Shipp
authors: Department of Chemistry and Biochemistry and.
authors: Ian R
authors: IR
authors: Gould
authors: Department of Chemistry and Biochemistry andSchool of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287.
authors: Everett L
authors: EL
authors: Shock
authors: School of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287.
authors: Lynda B
authors: LB
authors: Williams
authors: Department of Chemistry and Biochemistry andSchool of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287 h.hartnett@asu.edu.
authors: Hilairy E
authors: HE
authors: Hartnett
mesh_terms: D002384:Catalysis; D003510:Cyclohexanes / Q000737:chemistry; D055593:Geological Phenomena; D006860:Hydrogen Bonding; D008903:Minerals / Q000737:chemistry; D008956:Models, Chemical; D009930:Organic Chemicals / Q000737:chemistry*; D055601:Organic Chemistry Phenomena; D000069497:Origin of Life; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry*; D017967:Zinc Compounds / Q000737:chemistry*
chemical_list: D003510:Cyclohexanes; D008903:Minerals; D009930:Organic Chemicals; D013440:Sulfides; D017967:Zinc Compounds; C031238:zinc sulfide
keywords: hydrothermal organic geochemistry; organic catalysis