Cationic Copper Hydride Clusters Arising from Oxidation of (Ph3P)6Cu6H6.

Author(s) Liu, S.; Eberhart, M.S.; Norton, J.R.; Yin, X.; Neary, M.C.; Paley, D.W.
Journal J Am Chem Soc
Date Published 2017 May 30

Transfer of the first electron from (Ph3P)6Cu6H6 to Cp*2Fe(+) is fast (k > 106 L•mol(-1)•s(-1)). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 103 L•mol(-1)•s(-1). The second oxidation leads to the formation of [(Ph3P)6Cu6H5](+). The structure of [(Ph3P)6Cu6H5](+) has been confirmed by its conversion back to (Ph3P)6Cu6H6 and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(Ph3P)6Cu6H5](+) can also be prepared by treating (Ph3P)6Cu6H6 with MeOTf. With less than one equiv of Cp*2Fe(+) as oxidant, (Ph3P)6Cu6H6 gives [(Ph3P)7Cu7H6](+) as the major product; X-ray diffraction shows a Cu6 octahedron with one face capped by an additional Cu. [(Ph3P)7Cu7H6](+) can also be prepared by treating (Ph3P)6Cu6H6 with [Cu(CH3CN)4]+ (along with one equiv of Ph3P), and can also be converted back to (Ph3P)6Cu6H6 with base/H2.

DOI 10.1021/jacs.7b02183
ISSN 1520-5126
Citation J Am Chem Soc. 2017.

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