Electron transfer from hexameric copper hydrides

Michael S. Eberhart; Jack R. Norton; Ashley Zuzek; Wesley Sattler; Serge Ruccolo

doi:10.1021/ja408925m

Electron transfer from hexameric copper hydrides

Michael S. Eberhart, Jack R. Norton, Ashley Zuzek, Wesley Sattler, Serge Ruccolo

Research output: Contribution to journal › Article › peer-review

53 Scopus citations

Abstract

The octahedral core of 84-electron LCuH hexamers does not dissociate appreciably in solution, although their hydride ligands undergo rapid intramolecular rearrangement. The single-electron transfer proposed as an initial step in the reaction of these hexamers with certain substrates has been observed by stopped-flow techniques when [(Ph₃P)CuH]₆ is treated with a pyridinium cation. The same radical cation has been prepared by the oxidation of [(Ph₃P)CuH]₆ with Cp* ₂Fe⁺ and its reversible formation observed by cyclic voltammetry; its UV-vis spectrum has been confirmed by spectroelectrochemistry. The 48-electron trimer [(dppbz)CuH]₃ has been prepared by use of the chelating ligand 1,2-bis(diphenylphosphino)benzene (dppbz).

Original language	English (US)
Pages (from-to)	17262-17265
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	135
Issue number	46
DOIs	https://doi.org/10.1021/ja408925m
State	Published - Nov 20 2013
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Electron transfer from hexameric copper hydrides",

abstract = "The octahedral core of 84-electron LCuH hexamers does not dissociate appreciably in solution, although their hydride ligands undergo rapid intramolecular rearrangement. The single-electron transfer proposed as an initial step in the reaction of these hexamers with certain substrates has been observed by stopped-flow techniques when [(Ph3P)CuH]6 is treated with a pyridinium cation. The same radical cation has been prepared by the oxidation of [(Ph3P)CuH]6 with Cp* 2Fe+ and its reversible formation observed by cyclic voltammetry; its UV-vis spectrum has been confirmed by spectroelectrochemistry. The 48-electron trimer [(dppbz)CuH]3 has been prepared by use of the chelating ligand 1,2-bis(diphenylphosphino)benzene (dppbz).",

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T1 - Electron transfer from hexameric copper hydrides

AU - Eberhart, Michael S.

AU - Norton, Jack R.

AU - Zuzek, Ashley

AU - Sattler, Wesley

AU - Ruccolo, Serge

PY - 2013/11/20

Y1 - 2013/11/20

N2 - The octahedral core of 84-electron LCuH hexamers does not dissociate appreciably in solution, although their hydride ligands undergo rapid intramolecular rearrangement. The single-electron transfer proposed as an initial step in the reaction of these hexamers with certain substrates has been observed by stopped-flow techniques when [(Ph3P)CuH]6 is treated with a pyridinium cation. The same radical cation has been prepared by the oxidation of [(Ph3P)CuH]6 with Cp* 2Fe+ and its reversible formation observed by cyclic voltammetry; its UV-vis spectrum has been confirmed by spectroelectrochemistry. The 48-electron trimer [(dppbz)CuH]3 has been prepared by use of the chelating ligand 1,2-bis(diphenylphosphino)benzene (dppbz).

AB - The octahedral core of 84-electron LCuH hexamers does not dissociate appreciably in solution, although their hydride ligands undergo rapid intramolecular rearrangement. The single-electron transfer proposed as an initial step in the reaction of these hexamers with certain substrates has been observed by stopped-flow techniques when [(Ph3P)CuH]6 is treated with a pyridinium cation. The same radical cation has been prepared by the oxidation of [(Ph3P)CuH]6 with Cp* 2Fe+ and its reversible formation observed by cyclic voltammetry; its UV-vis spectrum has been confirmed by spectroelectrochemistry. The 48-electron trimer [(dppbz)CuH]3 has been prepared by use of the chelating ligand 1,2-bis(diphenylphosphino)benzene (dppbz).

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Electron transfer from hexameric copper hydrides

Abstract

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