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Hydride ions in oxide hosts hidden by hydroxide ions.

ABSTRACT: The true oxidation state of formally 'H(-)' ions incorporated in an oxide host is frequently discussed in connection with chemical shifts of (1)H nuclear magnetic resonance spectroscopy, as they can exhibit values typically attributed to H(+). Here we systematically investigate the link between geometrical structure and chemical shift of H(-) ions in an oxide host, mayenite, with a combination of experimental and ab initio approaches, in an attempt to resolve this issue. We demonstrate that the electron density near the hydrogen nucleus in an OH(-) ion (formally H(+) state) exceeds that in an H(-) ion. This behaviour is the opposite to that expected from formal valences. We deduce a relationship between the chemical shift of H(-) and the distance from the H(-) ion to the coordinating electropositive cation. This relationship is pivotal for resolving H(-) species that are masked by various states of H(+) ions.

SUBMITTER: Hayashi K

PROVIDER: S-EPMC3973043 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Hydride ions in oxide hosts hidden by hydroxide ions.

Hayashi Katsuro K Sushko Peter V PV Hashimoto Yasuhiro Y Shluger Alexander L AL Hosono Hideo H

Nature communications 20140324

The true oxidation state of formally 'H(-)' ions incorporated in an oxide host is frequently discussed in connection with chemical shifts of (1)H nuclear magnetic resonance spectroscopy, as they can exhibit values typically attributed to H(+). Here we systematically investigate the link between geometrical structure and chemical shift of H(-) ions in an oxide host, mayenite, with a combination of experimental and ab initio approaches, in an attempt to resolve this issue. We demonstrate that the ...[more]

PMID: 24662678

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Hydride ions in oxide hosts hidden by hydroxide ions.

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Hydride ions in oxide hosts hidden by hydroxide ions.

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