9 research outputs found

    Testing Hereditary Properties of Sequences

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    A hereditary property of a sequence is one that is preserved when restricting to subsequences. We show that there exist hereditary properties of sequences that cannot be tested with sublinear queries, resolving an open question posed by Newman et al. This proof relies crucially on an infinite alphabet, however; for finite alphabets, we observe that any hereditary property can be tested with a constant number of queries

    Variable Pathways for Oxygen Atom Insertion into Metal–Carbon Bonds: The Case of Cp*W(O)<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>)

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    Cp*W­(O)<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>) (<b>1</b>) (Cp* = η<sup>5</sup>-pentamethylcyclopentadienyl) reacts with oxygen atom donors (e.g., H<sub>2</sub>O<sub>2</sub>, PhIO, IO<sub>4</sub><sup>–</sup>) in THF/water to produce TMSCH<sub>2</sub>OH (TMS = trimethylsilyl). For the reaction of <b>1</b> with IO<sub>4</sub><sup>–</sup>, the proposed pathway for alcohol formation involves coordination of IO<sub>4</sub><sup>–</sup> to <b>1</b> followed by concerted migration of the −CH<sub>2</sub>TMS ligand to the coordinated oxygen of IO<sub>4</sub><sup>–</sup> with concomitant dissociation of IO<sub>3</sub><sup>–</sup> to produce Cp*W­(O)<sub>2</sub>(OCH<sub>2</sub>SiMe<sub>3</sub>) (<b>3</b>), which undergoes protonolysis to yield free alcohol. In contrast to the reaction with IO<sub>4</sub><sup>–</sup>, the reaction of <b>1</b> with H<sub>2</sub>O<sub>2</sub> results in the formation of the η<sup>2</sup>-peroxo complex Cp*W­(O)­(η<sup>2</sup>-O<sub>2</sub>)­(CH<sub>2</sub>SiMe<sub>3</sub>) (<b>2</b>). In the presence of acid (HCl) or base (NaOH), complex <b>2</b> produces TMSCH<sub>2</sub>OH. The conversion of <b>2</b> to TMSCH<sub>2</sub>OH catalyzed by Brønsted acid is proposed to occur through protonation of the η<sup>2</sup>-peroxo ligand, which facilitates the transfer of the −CH<sub>2</sub>TMS ligand to a coordinated oxygen of the η<sup>2</sup>-hydroperoxo ligand. In contrast, the hydroxide promoted conversion of <b>2</b> to TMSCH<sub>2</sub>OH is proposed to involve hydroxide coordination, followed by proton transfer from the hydroxide ligand to the peroxide ligand to yield a κ<sup>1</sup>-hydroperoxide intermediate. The migration of the −CH<sub>2</sub>TMS ligand to the coordinated oxygen of the κ<sup>1</sup>-hydroperoxo produces an alkoxide complex, which undergoes protonolysis to yield free alcohol

    The formation of low-temperature sedimentary pyrite and its relationship with biologically-induced processes

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    This contribution is an updated review on sedimentary pyrite and on its role in well-consolidated research topics, such as the biogeochemical cycles and the studies on sediment-hosted ore deposit studies, as well as new frontiers of research, such as astrobiology. Textural and compositional information preserved in sedimentary pyrite from sediment-hosted ore deposits has contributed to elucidate their environment of forzmation. In particular, the content of redox-sensitive elements such as Ni, Co, Mo, and V has implications for defining the syn- and post-sedimentary conditions. In addition, the stable isotope compositions are useful indicators of the pathways of both biogenic and abiogenic pyrite formation. Despite the longstanding research on pyrite and the mechanism of its formation, there are still significant gaps in our knowledge. In this nonexhaustive review, we briefly touch on different current aspects of research on sedimentary pyrite, exemplifying how sedimentary pyrite remains relevant to geoscientists, and becomes more and more relevant in understanding some basic aspects of knowledge, such as the origin of life and the search for extraterrestrial life, as well as aspect of classical applied science, such as the implications for ore deposition

    TIN ORGANOMETALLIC COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATA: PART II. DIMERIC DERIVATIVES

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